CN114930504A - Curable resin film, composite sheet, and method for producing semiconductor chip - Google Patents

Curable resin film, composite sheet, and method for producing semiconductor chip Download PDF

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Publication number
CN114930504A
CN114930504A CN202080090576.5A CN202080090576A CN114930504A CN 114930504 A CN114930504 A CN 114930504A CN 202080090576 A CN202080090576 A CN 202080090576A CN 114930504 A CN114930504 A CN 114930504A
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Prior art keywords
resin film
semiconductor chip
curable resin
wafer
meth
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CN202080090576.5A
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Inventor
篠田智则
根本拓
田村樱子
森下友尧
四宫圭亮
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Lintec Corp
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Lintec Corp
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Publication of CN114930504A publication Critical patent/CN114930504A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H01L23/3157—Partial encapsulation or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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    • H01—ELECTRIC ELEMENTS
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—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
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—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
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • B32B2037/268—Release layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/14—Semiconductor wafers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/11—Manufacturing methods

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  • Engineering & Computer Science (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dicing (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Laminated Bodies (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
  • Mechanical Engineering (AREA)
  • Container, Conveyance, Adherence, Positioning, Of Wafer (AREA)

Abstract

The present invention addresses the problem of providing a curable resin film that can form a protective film having excellent covering properties on both the bump formation surface and the side surface of a semiconductor chip. As a curable resin film for solving the problem, there is provided a curable resin film for forming a protective film on both the bump formation surface and the side surface of a semiconductor chip having a bump formation surface provided with bumps, the curable resin film satisfying the following condition (I). < condition (I) > a test piece of the curable resin film having a diameter of 25mm and a thickness of 1mm was strained under the conditions of a temperature of 90 ℃ and a frequency of 1Hz, and the storage modulus of the test piece was measured, and when the storage modulus of the test piece at a strain of 1% of the test piece was Gc1 and the storage modulus of the test piece at a strain of 300% of the test piece was Gc300, the X value calculated by the following formula (I) was 19 or more and less than 10,000. X is Gc1/Gc 300. cndot. (i).

Description

Curable resin film, composite sheet, and method for producing semiconductor chip
Technical Field
The present invention relates to a curable resin film, a composite sheet, and a method for manufacturing a semiconductor chip. More specifically, the present invention relates to a curable resin film, a composite sheet including the curable resin film, and a method for manufacturing a semiconductor chip provided with the cured resin film as a protective film by using these materials.
Background
In recent years, semiconductor devices have been manufactured by a mounting method called a so-called flip-chip (face down) method. In the flip-chip method, a semiconductor chip having bumps on a circuit surface and the semiconductor chip mounting substrate are stacked such that the circuit surface of the semiconductor chip faces the substrate, and the semiconductor chip is mounted on the substrate.
The semiconductor chip is generally obtained by dividing a semiconductor wafer having bumps on a circuit surface into individual pieces.
A semiconductor wafer having bumps is sometimes provided with a protective film for the purpose of protecting a bonding portion between the bumps and the semiconductor wafer (hereinafter, also referred to as a "bump neck portion").
For example, in patent documents 1 and 2, a protective film is formed by pressing and bonding a laminate, in which a support base, an adhesive layer, and a thermosetting resin layer are sequentially laminated, to a bump forming surface of a semiconductor wafer provided with bumps with the thermosetting resin layer as a bonding surface, and then heating and curing the thermosetting resin layer.
Documents of the prior art
Patent literature
Patent document 1: japanese laid-open patent publication No. 2015-092594
Patent document 2: japanese laid-open patent publication No. 2012-169484
Disclosure of Invention
Problems to be solved by the invention
In recent years, with the miniaturization and thinning of IC embedded products such as electronic devices, there is also a growing demand for the thinning of semiconductor chips. However, when the semiconductor chip is thinned, the strength of the semiconductor chip is reduced. Therefore, for example, when the semiconductor chip is transported or a subsequent process for packaging the semiconductor chip is performed, there is a problem that the semiconductor chip is easily broken.
Therefore, it is conceivable to form a protective film on the bump formation surface of the semiconductor wafer to protect the neck portion of the bump and to improve the strength of the semiconductor chip. However, the strength of the semiconductor chip cannot be sufficiently improved only by forming the protective film on the bump formation surface of the semiconductor wafer. In addition, the protective film may be peeled off.
Then, the present inventors conceived: by providing the protective film for protecting the neck portion of the bump not only on the bump forming surface but also on the side surface of the semiconductor chip, the strength of the semiconductor chip can be improved, and the peeling of the protective film can be suppressed, so that an extremely rational structure can be constructed. Based on such an idea, the present inventors have made extensive studies and have created a curable resin film capable of forming a protective film having excellent covering properties on both the bump formation surface and the side surface of the semiconductor chip.
Accordingly, an object of the present invention is to provide a curable resin film capable of forming a protective film excellent in covering properties on both a bump formation surface and a side surface of a semiconductor chip, a composite sheet provided with the curable resin film, and a method for manufacturing a semiconductor chip using these materials (the curable resin film and the composite sheet).
Means for solving the problems
As a result of intensive studies, the present inventors have found that the above problems can be solved by focusing attention on parameters which can be calculated from specific physical property values possessed by a curable resin film, and have completed the present invention.
Namely, the present invention relates to the following [1] to [14 ].
[1] A curable resin film for forming a cured resin film as a protective film on both a bump formation surface and a side surface of a semiconductor chip having a bump formation surface provided with a bump, the curable resin film satisfying the following condition (I).
< Condition (I) >
A test piece of the curable resin film having a diameter of 25mm and a thickness of 1mm is strained at a temperature of 90 ℃ and a frequency of 1Hz, and the storage modulus of the test piece is measured, and when the storage modulus of the test piece at a strain of 1% of the test piece is Gc1 and the storage modulus of the test piece at a strain of 300% of the test piece is Gc300, the value X calculated by the following formula (i) is 19 or more and less than 10,000.
X＝Gc1/Gc300····(i)
[2] The curable resin film according to [1], wherein,
in the above condition (I), Gc300 is less than 15,000.
[3] A composite sheet for forming a cured resin film as a protective film on both the bump formation surface and the side surface of a semiconductor chip having a bump formation surface provided with bumps,
the composite sheet has a laminated structure in which a support sheet and a layer of a curable resin are laminated,
the curable resin is the curable resin film according to [1] or [2 ].
[4] A method of use, the method comprising:
the curable resin film according to [1] or [2] above is used for forming a cured resin film as a protective film on both the bump formation surface and the side surface of a semiconductor chip having a bump formation surface provided with bumps.
[5] A method of use, the method comprising:
the composite sheet according to [3] above is used for forming a cured resin film as a protective film on both the bump formation surface and the side surface of a semiconductor chip having a bump formation surface provided with bumps.
[6] A method for manufacturing a semiconductor chip, comprising the following steps (S1) to (S4) in this order,
step (S1): preparing a wafer for manufacturing a semiconductor chip, in which a groove portion as a line to divide the wafer is formed on a bump formation surface of a semiconductor wafer having the bump formation surface, so as not to reach a back surface of the wafer;
step (S2): pressing and adhering a first curable resin (x1) to the bump formation surface of the semiconductor chip production wafer, and filling the first curable resin (x1) into the groove portion formed in the semiconductor chip production wafer while covering the bump formation surface of the semiconductor chip production wafer with the first curable resin (x 1);
step (S3): curing the first curable resin (x1) to obtain a wafer for manufacturing a semiconductor chip with a first cured resin film (r 1);
step (S4): obtaining a semiconductor chip in which at least the bump formation surface and the side surface are covered with the first cured resin film (r1) by singulating the semiconductor chip-producing wafer with the first cured resin film (r1) along the planned dividing lines,
after the step (S2) and before the step (S3), after the step (S3) and before the step (S4), or in the step (S4), the method further comprises the step (S-BG),
step (S-BG): grinding the back surface of the wafer for manufacturing semiconductor chips,
the curable resin film according to [1] or [2] is used as the first curable resin (x 1).
[7] The method for manufacturing a semiconductor chip according to item 6 above, wherein,
the step (S2) is performed as follows: a first composite sheet (alpha 1) having a laminate structure in which a first support sheet (Y1) and a layer (X1) of the first curable resin (X1) are laminated is pressed against the bump formation surface of the semiconductor chip production wafer with the layer (X1) as a bonding surface and bonded thereto.
[8] The method for manufacturing a semiconductor chip according to item [7], wherein,
the step (S-BG) is included after the step (S2) and before the step (S3),
the step (S-BG) is performed as follows: grinding the back surface of the wafer for manufacturing semiconductor chips with the first composite sheet (alpha 1) attached, and then peeling the first support sheet (Y1) from the first composite sheet (alpha 1),
the step (S4) is performed by: and cutting the part of the first cured resin film (r1) formed in the groove part of the wafer for manufacturing the semiconductor chip with the first cured resin film (r1) along the planned dividing line.
[9] The method for manufacturing a semiconductor chip according to item [7], wherein,
the step (S-BG) is included after the step (S3) and before the step (S4),
the step (S3) is performed without peeling the first support sheet (Y1) from the first composite sheet (alpha 1),
the step (S-BG) is performed as follows: grinding the back surface of the wafer for manufacturing semiconductor chips with the first composite sheet (alpha 1) attached, and then peeling the first support sheet (Y1) from the first composite sheet (alpha 1),
the step (S4) is performed by: and cutting the part of the first cured resin film (r1) formed in the groove part of the wafer for manufacturing the semiconductor chip with the first cured resin film (r1) along the planned dividing line.
[10] The method for manufacturing a semiconductor chip according to item [7], wherein,
the step (S-BG) is included after the step (S3) and before the step (S4),
peeling the first support sheet (Y1) from the first composite sheet (alpha 1) after the step (S2) and before the step (S3),
the step (S-BG) is performed as follows: sticking a back grinding sheet (b-BG) to the surface of the first cured resin film (r1) of the semiconductor chip production wafer with the first cured resin film (r1), grinding the back surface of the semiconductor chip production wafer in a state where the back grinding sheet (b-BG) is stuck, and then peeling the back grinding sheet (b-BG) from the semiconductor chip production wafer with the first cured resin film (r1),
the step (S4) is performed by: and cutting the part of the first cured resin film (r1) formed in the groove part of the wafer for manufacturing the semiconductor chip with the first cured resin film (r1) along the planned dividing line.
[11] The method for manufacturing a semiconductor chip according to item [7], wherein,
the step (S4) includes the step (S-BG),
peeling the first support sheet (Y1) from the first composite sheet (alpha 1) after the step (S2) and before the step (S3),
the step (S4) is performed as follows: cutting a notch along the planned dividing line in a portion of the first cured resin film (r1) of the semiconductor chip-manufacturing wafer with the first cured resin film (r1) formed in the groove portion, or after forming a modified region along the planned dividing line, attaching a back grinding sheet (b-BG) to a surface of the first cured resin film (r1) of the semiconductor chip-manufacturing wafer with the first cured resin film (r1) as the step (S-BG), and grinding the back surface of the semiconductor chip-manufacturing wafer while the back grinding sheet (b-BG) is attached.
[12] The method for manufacturing a semiconductor chip according to any one of [6] to [11], further comprising the following step (T).
Step (T): a step of forming a second cured resin film (r2) on the back surface of the wafer for manufacturing semiconductor chips
[13] The method for manufacturing a semiconductor chip according to any one of [6] to [12], wherein the width of the groove is 10 μm to 2000 μm.
[14] The method for manufacturing a semiconductor chip according to any one of [6] to [13], wherein the depth of the groove is 30 μm to 700 μm.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a curable resin film capable of forming a protective film excellent in covering properties with respect to both a bump formation surface and a side surface of a semiconductor chip, a composite sheet provided with the curable resin film, and a method for manufacturing a semiconductor chip using these materials (the curable resin film and the composite sheet).
Drawings
Fig. 1 is a schematic cross-sectional view of the first curable resin film (x 1).
Fig. 2 is a plan view schematically illustrating the amount of overflow of the resin film when the planar shape of the resin film is circular.
Fig. 3 is a schematic cross-sectional view showing the configuration of the first composite sheet (α 1) used in the manufacturing method of the present invention.
FIG. 4 is a schematic cross-sectional view showing an example of a specific configuration of the first composite sheet (. alpha.1).
FIG. 5 is a schematic sectional view showing another example of a specific configuration of the first composite sheet (. alpha.1).
Fig. 6 is a schematic sectional view showing another example of the specific configuration of the first composite sheet (α 1).
Fig. 7 is a process diagram of a method for manufacturing a semiconductor chip according to the present invention.
Fig. 8 is a plan view showing an example of the wafer for manufacturing a semiconductor chip prepared in the step (S1).
Fig. 9 is a schematic cross-sectional view showing an example of the wafer for manufacturing a semiconductor chip prepared in the step (S1).
Fig. 10 is a diagram showing an outline of the step (S2).
Fig. 11 is a diagram showing an outline of the manufacturing method of the first embodiment.
Fig. 12 is a diagram showing an outline of the manufacturing method of the second embodiment.
Fig. 13 is a diagram showing an outline of the manufacturing method of the third embodiment.
Fig. 14 is a diagram showing an outline of the manufacturing method of the fourth embodiment.
Fig. 15 is a plan view schematically showing a laminate including the first thermosetting resin film (x1-1) produced when the amount of overflow of the first thermosetting resin film (x1-1) was measured.
Fig. 16 is a photograph for replacing drawings showing the results of cross-sectional observation showing filling properties of the grooves in examples 1 and 2 and comparative example 1.
Description of the symbols
10 wafer for manufacturing semiconductor chip
11 wafer
11a bump formation surface
11b back side
12 bump
13 groove part
40 semiconductor chip
x1 first curable resin
r1 first cured resin film
Layer of X1
Y1 first support sheet
Alpha 1 first composite sheet
x2 second curable resin
r2 second cured resin film
Layer of X2
Y2 second support sheet
Alpha 2 second composite sheet
51 base material
61 adhesive layer
71 intermediate layer
Detailed Description
In the present specification, the "active ingredient" refers to a component other than a diluting solvent such as water or an organic solvent among components contained in a target composition.
In the present specification, the weight average molecular weight and the number average molecular weight are values in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method.
In the present specification, regarding a preferable numerical range (for example, a range of contents or the like), lower limit values and upper limit values described hierarchically may be independently combined. For example, according to the description of "preferably 10 to 90, more preferably 30 to 60", the "preferable lower limit value (10)" and the "more preferable upper limit value (60)" may be combined to obtain "10 to 60".
[ curable resin film (first curable resin film (x1)) ]
The curable resin film of the present invention is used for forming a cured resin film as a protective film on both the bump formation surface and the side surface of a semiconductor chip having a bump formation surface provided with a bump, and satisfies the following condition (I).
< Condition (I) >
A test piece of the curable resin film having a diameter of 25mm and a thickness of 1mm is strained at a temperature of 90 ℃ and a frequency of 1Hz, and the storage modulus of the test piece is measured, and when the storage modulus of the test piece at a strain of 1% of the test piece is Gc1 and the storage modulus of the test piece at a strain of 300% of the test piece is Gc300, the value X calculated by the following formula (i) is 19 or more and less than 10,000.
X＝Gc1/Gc300····(i)
The test piece for measuring the storage modulus has a film shape and a circular planar shape.
The test piece may be a single layer of the curable resin film having a thickness of 1mm, but from the viewpoint of ease of production, a laminated film formed by laminating a plurality of single layers of the curable resin film having a thickness of less than 1mm is preferable.
The thickness of the curable resin films constituting a single layer of the plurality of laminated films may be the same or different from each other, or may be partially the same, but it is preferable that the thickness of the curable resin films is the same from the viewpoint of ease of production.
In the present specification, the term "storage modulus of a test piece" means "storage modulus of a test piece corresponding to strain when strain is applied to a test piece of a resin film having a diameter of 25mm and a thickness of 1mm under the conditions of a temperature of 90 ℃ and a frequency of 1 Hz" without being limited to Gc1 and Gc 300.
The curable resin film according to one embodiment of the present invention may constitute a composite sheet having a laminated structure in which a support sheet and a layer of the curable resin film are laminated, for example.
In the present specification, a curable resin film (curable resin film of the present invention) for forming a cured resin film as a protective film on both a bump formation surface and a side surface of a semiconductor chip is also referred to as a "first curable resin film (x 1)" or a "first curable resin (x 1)". Further, a cured resin film formed by curing the "first curable resin film (x 1)" or the "first curable resin (x 1)" is also referred to as a "first cured resin film (r 1)". The curable resin film for forming a cured resin film as a protective film on the surface (back surface) of the semiconductor chip opposite to the bump formation surface is also referred to as "second curable resin film (x 2)" or "second curable resin (x 2)". Further, a cured resin film formed by curing the "second curable resin film (x 2)" or the "second curable resin (x 2)" is also referred to as a "second cured resin film (r 2)".
In the present specification, a composite sheet for forming a first cured resin film (r1) as a protective film on both a bump formation surface and a side surface of a semiconductor chip is also referred to as a "first composite sheet (α 1)". The "first composite sheet (α 1)" has a laminated structure in which a "first support sheet (Y1)" and a "layer (X1) of a first curable resin (X1)" are laminated.
A composite sheet for forming a second cured resin film (r2) as a protective film on the back surface of the semiconductor chip is also referred to as a "second composite sheet (α 2)". The "second composite sheet (α 2)" has a laminated structure in which the "second support sheet (Y2)" and the "layer (X2) of the second curable resin (X2)" are laminated.
Fig. 1 shows a schematic cross-sectional view of the first curable resin film (x 1).
In the drawings used in the following description, for the purpose of facilitating understanding of the features of the present invention, a part which is a main part may be enlarged for convenience, and the dimensional ratios of the respective components are not necessarily the same as the actual ones.
The first curable resin film (x1) shown in fig. 1 includes a1 st release film 151 on one surface (in this specification, sometimes referred to as "1 st surface") x1a, and a2 nd release film 152 on the other surface (in this specification, sometimes referred to as "2 nd surface") x1b opposite to the 1 st surface x1 a.
The first curable resin film (x1) having such a configuration is suitable for storage in the form of, for example, a roll.
Both the 1 st release film 151 and the 2 nd release film 152 are known.
The 1 st release film 151 and the 2 nd release film 152 may be the same as or different from each other. Examples of the case where the 1 st release film 151 and the 2 nd release film 152 are different include a case where the peeling force required for peeling from the first curable resin film (x1) is different.
In the first curable resin film (x1) shown in fig. 1, either the 1 st release film 151 or the 2 nd release film 152 is removed, and the exposed surface thus generated becomes an attachment surface to an attachment object. Further, the remaining one of the 1 st release film 151 and the 2 nd release film 152 is removed, and the exposed surface thus generated becomes a bonding surface for a first support sheet (Y1) constituting a first composite sheet (α 1) described later.
Fig. 1 shows an example in which a release film is provided on both surfaces (the 1 st surface x1a and the 2 nd surface x1b) of the first curable resin film (x1), but the release film may be provided only on one surface of the first curable resin film (x1), that is, only on the 1 st surface x1a or only on the 2 nd surface x1 b.
The first curable resin film (x1) may be any of thermosetting and energy ray-curable films, and may have both thermosetting and energy ray-curable characteristics.
In the present specification, "energy rays" refer to those having energy quanta in an electromagnetic wave or a charged particle beam. Examples of the energy ray include ultraviolet rays, radiation, and electron beams. The ultraviolet rays can be irradiated using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet light source. The electron beam may irradiate an electron beam generated by an electron beam accelerator or the like.
In the present specification, "energy ray-curable property" indicates a property that curing occurs by irradiation with an energy ray, and "non-energy ray-curable property" indicates a property that curing does not occur even when irradiated with an energy ray.
The first curable resin film (x1) contains a resin component.
The first curable resin film (x1) may or may not contain a component other than the resin component, in addition to the resin component.
Preferred embodiments of the first curable resin film (x1) include, for example: a resin component, a filler, and various additives which do not belong to any of these (resin component and filler) and which have an effect of adjusting the storage modulus of the first curable resin film (x 1).
Examples of the additive having an effect of adjusting the storage modulus of the first curable resin film (x1) include: rheology modifiers (thixotropic agents), surfactants, silicone oils, and the like.
The first curable resin film (x1) is soft and suitable for use in bonding to an object having an uneven surface, such as a wafer for manufacturing a semiconductor chip having a bump forming surface provided with bumps and grooves as lines to be divided.
In the following description, the "semiconductor chip manufacturing wafer having a bump forming surface provided with bumps and grooves as lines to be divided" will also be simply referred to as "semiconductor chip manufacturing wafer".
The first curable resin film (x1) is pressed against the bump formation surface of the wafer for manufacturing semiconductor chips and is bonded thereto, whereby the groove portions can be filled with the first curable resin film (x1) with good filling properties.
Further, the first curable resin film (x1) is pressed against the bump formation surface of the wafer for manufacturing semiconductor chips and bonded thereto, the bump penetrates through the first curable resin film (x1), and the top of the bump protrudes from the first curable resin film (x 1). Further, the first curable resin film (x1) spreads between the bumps so as to cover the bumps, comes into close contact with the bump forming surface, and covers the surfaces of the bumps, particularly the surfaces of the portions in the vicinity of the bump forming surface to fill the bases of the bumps. In this state, the first curable resin film (x1) is prevented from remaining on the top of the bump, including the top of the bump. Therefore, the first curable resin film (r1) which is a cured product of the first curable resin film (x1) is prevented from adhering to the upper portions of the bumps. Further, even after the first curable resin film (x1) is attached to the object to be attached, the area of the first curable resin film (x1) at the beginning (before attachment) is easily maintained, and a phenomenon in which the area after attachment is enlarged compared to the area of the first curable resin film (x1) at the beginning (before attachment) (hereinafter, also referred to as "overflow") is suppressed. Therefore, when the first curable resin film (x1) is bonded to the bump formation surface of the wafer for manufacturing semiconductor chips, filling defects and the like into the groove portions and the base portions of the bumps are also suppressed.
Further, when the first curable resin film (x1) is used, the first curable resin film (x1) and the first cured resin film (r1) which is a cured product thereof are provided on the bump formation surface, and thus, the region other than the upper portion of the bump or the region near the bump on the bump formation surface can be prevented from being exposed to an unintended extent (hereinafter, also referred to as "shrinkage cavity").
These effects can be achieved by setting the value of X defined in the above condition (I) to 19 or more and less than 10,000.
The presence or absence of the first curable resin film (x1) or the first curable resin film (r1) remaining on the upper portion of the bump can be confirmed as follows: for example, the top of the bump is observed with an optical microscope or SEM (scanning electron microscope) to acquire imaging data.
The presence or absence of the overflow of the first curable resin film (x1) can be observed by visual observation or the like.
Further, the presence or absence of a crater in the first curable resin film (x1) or the first curable resin film (r1) can be confirmed as follows: for example, the bump formation surface is observed with an optical microscope or SEM (scanning electron microscope) to acquire imaging data.
When a resin film such as the first curable resin film (x1) is stuck to the sticking object and a flow-out occurs, the flow-out amount can be calculated by the following method.
That is, the resin film in a state where the overflow occurred is viewed from above downward in plan, and the maximum value of the length of the line segment connecting two different points on the outer periphery of the resin film at this time is obtained. Further, a value of the width of the resin film at the first (i.e., before the occurrence of the overflow) at a position overlapping the line segment showing the maximum value is obtained. Then, the resin film overflow amount can be calculated by subtracting the width of the resin film from the maximum value of the length of the line segment.
Fig. 2 is a plan view schematically illustrating the amount of overflow of the resin film when the planar shape of the resin film is circular.
The resin film 101 shown in fig. 2 is in a state of being stuck on the sticking object 102 and being protruded from the original size. The resin film of the initial size is shown in reference numeral 101' for the purpose of facilitating understanding of the amount of overflow. Here, the planar shape of the first resin film 101' is circular, but the planar shape of the resin film 101 formed in the overflowed state is non-circular. However, this is merely an example, and the planar shape of the overflow-formed part 101 is not limited to the shape shown here.
In order to determine the amount of overflow of the resin film 101, the length D of a line segment connecting one point 1010a and another point 1010b different from the one point on the outer periphery 1010 of the resin film 101 is determined 1 Then, the value D of the width of the resin film 101' at the first (i.e., before the overflow) at the position overlapping the line segment showing the maximum value is obtained 0 And (4) finishing. D 1 And D 0 Difference of difference (D) 1 -D 0 ) The overflow amount is defined as above.
In a planar view, the line segment indicating the maximum value in the resin film 101 may pass through the center of the circle in the first resin film 101 ', and in this case, the width of the first resin film 101 ' at the position overlapping the line segment indicating the maximum value is the diameter of the resin film 101 '.
Here, although the description has been given of the amount of overflow of the resin film when the planar shape of the resin film is a circular shape with reference to the drawings, the amount of overflow of the resin film may be calculated by the same method when the planar shape is other than a circular shape.
When the first curable resin film (x1) is attached to the bump formation surface of the semiconductor chip production wafer, the degree of strain of the curable resin film is greatly different between the intermediate stage when the first curable resin film (x1) starts to enter the groove portion while the upper portion of the bump penetrates through the first curable resin film (x1) and protrudes, and the final stage when the first curable resin film (x1) fills the groove portion while filling the base portion of the bump. More specifically, the strain of the first curable resin film (x1) in the intermediate stage is small, and the strain of the first curable resin film (x1) in the final stage is large.
The excellent effects described above can be achieved by limiting the value of X (Gc 1/Gc300) defined under the above condition (I) to 19 or more and less than 10,000 by using Gc1 as the storage modulus when the strain is small and Gc300 as the storage modulus when the strain is large, and by using Gc1 as the storage modulus when the strain is large and using Gc300 as the storage modulus when the strain is large for the first curable resin film (X1).
From the viewpoint of more easily exerting the effect of the present invention, the upper limit of the X value defined in the above condition (I) of the first curable resin film (X1) is preferably 5000 or less, more preferably 2000 or less, further preferably 1000 or less, further preferably 500 or less, further more preferably 300 or less, further preferably 100 or less, and further preferably 70 or less.
In addition, from the viewpoint of further improving the filling property into the groove portion of the wafer for manufacturing a semiconductor chip in the effect of the present invention, the value X defined in the above condition (I) is preferably 25 or more, more preferably 30 or more, further preferably 40 or more, further preferably 50 or more, and further more preferably 60 or more.
The first curable resin film (X1) is not particularly limited as long as Gc1 has an X value of 19 or more and less than 10000, which is defined in the above condition (I).
Among them, Gc1 is preferably 1 × 10 from the viewpoint of more easily exhibiting the effect of the present invention 4 ～1×10 6 Pa, more preferably 3X 10 4 ～7×10 5 Pa, more preferably 5X 10 4 ～5×10 5 Pa。
The first curable resin film (X1) is not particularly limited as long as Gc300 has an X value of 19 or more and less than 10000.
Among them, Gc300 is preferably less than 15,000Pa, more preferably 10,000Pa or less, further preferably 5,000Pa or less, further preferably 4,000Pa or less, and further more preferably 3,500Pa or less, from the viewpoint of making the filling property into the grooves of the wafer for manufacturing a semiconductor chip more favorable in the effect of the present invention. In addition, Gc300 is preferably 100Pa or more, more preferably 500Pa or more, and further preferably 1,000Pa or more, from the viewpoint of suppressing the shrinkage cavity of the first curable resin film (x 1).
It is preferable that the first curable resin film (X1) satisfy the X value defined in the above condition (I) and one or both of Gc1 and Gc300 satisfy the above range.
The storage modulus of the first curable resin film (x1) is not limited to Gc1 and Gc300, and can be easily adjusted by adjusting one or both of the type and the content of the component contained in the first curable resin film (x 1). Therefore, one or both of the type and the content of the component contained in the composition for forming the first curable resin film (x1) may be adjusted. For example, when the first thermosetting resin film-forming composition (x1-1-1) described later is used, the storage modulus of the first curable resin film (x1) can be easily adjusted by adjusting one or both of the type and content of the main components such as the polymer component (a) and the filler (D) in the composition, and adjusting one or both of the type and content of the additive (I) selected from one or more of a rheology modifier, a surfactant, and silicone oil.
For example, when the content of one or both of the filler (D) and the additive (I) in the first curable resin film (X1) and the first curable resin film-forming composition is increased, it is easy to adjust the Gc1 to a large value, and as a result, it is easy to adjust the X value to a large value.
The first curable resin film (x1) may be composed of one layer (single layer) or may be composed of a plurality of layers including two or more layers. When the first curable resin film (x1) is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.
In the present specification, the phrase "the plurality of layers may be the same or different from each other" means "all the layers may be the same or different from each other or only some of the layers may be different from each other", and "the plurality of layers are different from each other" means "at least one of the constituent material and the thickness of each layer is different from each other", in addition to the case of the first curable resin film (x 1).
From the viewpoint of improving the encapsulation property of the bump formation surface of the semiconductor wafer for semiconductor chip production and from the viewpoint of improving the filling property into the grooves of the semiconductor wafer for semiconductor chip production, the thickness of the first curable resin film (x1) is preferably 10 μm or more, more preferably 20 μm or more, further preferably 30 μm or more, and further preferably more than 30 μm. Further, it is preferably 200 μm or less, more preferably 150 μm or less, further preferably 130 μm or less, further preferably 100 μm or less, further more preferably 80 μm or less.
Here, "the thickness of the layer (X1) of the first curable resin (X1)" means the thickness of the entire layer (X1), and for example, the thickness of the layer (X1) composed of a plurality of layers means the total thickness of all layers constituting the layer (X1).
Here, "the thickness of the first curable resin film (x 1)" means the thickness of the entire first curable resin film (x1), and for example, the thickness of the first curable resin film (x1) composed of a plurality of layers means the total thickness of all the layers constituting the first curable resin film (x 1).
< composition for Forming first curable resin film >
The first curable resin film (x1) can be formed using a first curable resin film-forming composition containing the constituent materials thereof. For example, the first curable resin film (x1) can be formed by applying the first curable resin film-forming composition to the formation target surface and drying it as necessary. The content ratio of the components that do not vaporize at normal temperature in the first curable resin film-forming composition is generally the same as the content ratio of the components in the first curable resin film (x 1). In the present specification, "normal temperature" refers to a temperature at which cooling or heating is not particularly performed, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ℃.
The first thermosetting resin film (x1-1) can be formed using the first thermosetting resin film-forming composition (x1-1-1), and the first energy ray-curable resin film (x1-2) can be formed using the first energy ray-curable resin film-forming composition (x 1-2-1). In the present specification, when the first curable resin film (x1) has both properties of thermosetting and energy ray-curable properties, the first curable resin film (x1) is treated as a thermosetting resin film when the contribution of thermosetting of the first curable resin film (x1) is larger than the contribution of energy ray-curing with respect to the first curable resin film (r1) formed by curing thereof. In contrast, in the case where the contribution of energy ray curing of the first curable resin film (x1) is larger than the contribution of thermal curing with respect to the curing thereof, the first curable resin film (x1) is treated as an energy ray-curable resin film.
The first curable resin film-forming composition may be applied by a known method, and examples thereof include methods using various coaters such as a spin coater, a spray coater, an air knife coater, a bar coater, a gravure coater, a roll coater, a curtain coater, a die coater, a knife coater, a screen coater, a meyer bar coater, and a kiss coater.
The drying conditions of the curable resin film-forming composition are not particularly limited, regardless of whether the first curable resin film (x1) is a thermosetting resin film or an energy ray-curable resin film. When the first curable resin film-forming composition contains a solvent described later, it is preferably dried by heating. Further, the solvent-containing composition for forming a curable resin film is preferably dried by heating at 70 to 130 ℃ for 10 seconds to 5 minutes, for example. The first thermosetting resin film-forming composition (x1-1-1) is preferably dried by heating so as not to cause thermosetting of the composition itself and the first thermosetting resin film (x1-1) formed from the composition.
Hereinafter, the first thermosetting resin film (x1-1) and the first energy ray-curable resin film (x1-2) will be described in more detail.
< first thermosetting resin film (x1-1) >
When the first cured resin film (r1) is formed as a cured product by curing the first thermosetting resin film (x1-1), the curing conditions are not particularly limited as long as the cured product has a degree of cure sufficient to exert its function, and may be appropriately selected depending on the type of the first thermosetting resin film (x1-1), the application of the cured product, and the like.
The heating temperature of the first thermosetting resin film (x1-1) during curing is preferably 100 to 200 ℃, more preferably 110 to 170 ℃, and particularly preferably 120 to 150 ℃. The heating time in the thermosetting is preferably 0.5 to 5 hours, more preferably 0.5 to 4 hours, and particularly preferably 1 to 3 hours.
< first thermosetting resin film-forming composition (x1-1-1) >
Examples of the first thermosetting resin film-forming composition (x1-1-1) include a first thermosetting resin film-forming composition (x1-1-1) (in the present specification, it may be abbreviated as "composition (x 1-1-1)") containing a polymer component (a), a thermosetting component (B), a filler (D), and an additive (I).
(Polymer component (A))
The polymer component (a) is a polymer compound for imparting film formability, flexibility, and the like to the first thermosetting resin film (x 1-1). The polymer component (a) has thermoplasticity and does not have thermosetting property. It should be noted that, in the present specification, the polymer compound also includes a product of polycondensation reaction.
The polymer component (a) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the polymer component (a) include: polyvinyl acetal, acrylic resin, urethane resin, phenoxy resin, silicone resin, saturated polyester resin, and the like.
Among these, the polymer component (a) is preferably polyvinyl acetal from the viewpoint of easily adjusting Gc300 to an appropriate value and thus adjusting the X value to an appropriate value.
The polyvinyl acetal in the polymer component (a) may be a known polyvinyl acetal.
Among these, preferable polyvinyl acetals include, for example, polyvinyl formal and polyvinyl butyral, and more preferably polyvinyl butyral.
Examples of the polyvinyl butyral include polyvinyl butyrals having structural units represented by the following formulae (i) -1, (i) -2, and (i) -3.
[ chemical formula 1]
Figure BDA0003714954500000151
(wherein l, m and n are each independently an integer of 1 or more.)
The polyvinyl acetal preferably has a weight average molecular weight (Mw) of 5,000 to 200,000, more preferably 8,000 to 100,000. When the weight average molecular weight of the polyvinyl acetal is in such a range, the effect of suppressing the first thermosetting resin film (x1-1) from remaining on the upper portion of the bump, the effect of suppressing the first thermosetting resin film (x1-1) from overflowing, the effect of suppressing the first thermosetting resin film (x1-1) and the shrinkage cavity of the cured product thereof on the bump formation surface, and the effect of improving the filling property of the first thermosetting resin film (x1-1) into the groove portion are further improved when the first thermosetting resin film (x1-1) is attached to the bump formation surface of the semiconductor chip production wafer.
The glass transition temperature (Tg) of the polyvinyl acetal is preferably 40 to 80 ℃, more preferably 50 to 70 ℃. When the Tg of the polyvinyl acetal is in such a range, the effect of suppressing the first thermosetting resin film (x1-1) from remaining on the upper portion of the bump, the effect of suppressing the first thermosetting resin film (x1-1) from overflowing, the effect of suppressing the first thermosetting resin film (x1-1) and shrinkage cavities of a cured product thereof on the bump formation surface, and the effect of improving the filling property of the first thermosetting resin film (x1-1) into the groove portion are further improved when the first thermosetting resin film (x1-1) is attached to the bump formation surface of the semiconductor chip production wafer.
The ratio of the three or more monomers constituting the polyvinyl acetal can be arbitrarily selected.
As the acrylic resin in the polymer component (a), a known acrylic polymer can be mentioned.
The weight average molecular weight (Mw) of the acrylic resin is preferably 5,000 to 1,000,000, more preferably 8,000 to 800,000. When the weight average molecular weight of the acrylic resin is in such a range, the effect of suppressing the first thermosetting resin film (x1-1) from remaining on the upper portion of the bump, the effect of suppressing the first thermosetting resin film (x1-1) from overflowing, the effect of suppressing the first thermosetting resin film (x1-1) and the shrinkage cavity of the cured product thereof on the bump formation surface, and the effect of improving the filling property of the first thermosetting resin film (x1-1) into the groove portion are further improved when the first thermosetting resin film (x1-1) is attached to the bump formation surface of the semiconductor chip production wafer.
The glass transition temperature (Tg) of the acrylic resin is preferably-50 to 70 ℃, and more preferably-30 to 60 ℃. When the Tg of the acrylic resin is in such a range, the effect of suppressing the first thermosetting resin film (x1-1) from remaining on the upper portion of the bump, the effect of suppressing the first thermosetting resin film (x1-1) from overflowing, the effect of suppressing the shrinkage of the first thermosetting resin film (x1-1) and its cured product on the bump formation surface, and the effect of improving the filling property of the first thermosetting resin film (x1-1) into the groove portion are further improved when the first thermosetting resin film (x1-1) is attached to the bump formation surface of the semiconductor chip production wafer.
In the case where the acrylic resin has two or more kinds of structural units, the glass transition temperature (Tg) of the acrylic resin can be calculated using the Fox equation. The Tg of the monomer used for deriving the structural unit can be a value described in a polymer data manual (polymers データ and ハンドブック) or an adhesive manual (tack ハンドブック).
The acrylic resin may be composed of only one monomer, or two or more monomers, and when two or more monomers are used, the combination and ratio of the monomers can be arbitrarily selected.
Examples of the acrylic resin include:
one or two or more polymers of (meth) acrylic acid esters;
copolymers of two or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide;
one or more (meth) acrylates, and copolymers with one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide.
In the present specification, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". The same applies to terms similar to those of (meth) acrylic acid, for example, the "(meth) acrylate" is a concept including both "acrylate" and "methacrylate", and the "(meth) acryl" is a concept including both "acryl" and "methacryl".
Examples of the (meth) acrylate constituting the acrylic resin include: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, myristyl (meth) acrylate, Alkyl (meth) acrylates having a chain structure in which the alkyl group constituting the alkyl ester is 1 to 18 carbon atoms, such as pentadecyl (meth) acrylate, hexadecyl (meth) acrylate ((palm (meth) acrylate)), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate ((stearyl (meth) acrylate);
cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
aralkyl (meth) acrylates such as benzyl (meth) acrylate;
cycloalkenyl (meth) acrylates such as dicyclopentenyl (meth) acrylate;
cycloalkenyloxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate;
(meth) acrylimide;
glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate;
hydroxyl group-containing (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate;
and substituted amino group-containing (meth) acrylates such as N-methylaminoethyl (meth) acrylate. Here, the "substituted amino group" refers to a group in which 1 or 2 hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom.
The acrylic resin may have a functional group capable of bonding with another compound, such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, or isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a crosslinking agent (F) described later, or may be directly bonded to another compound without the crosslinking agent (F). By bonding the acrylic resin to another compound through the functional group, for example, the reliability of the package obtained by using the first thermosetting resin film (x1-1) tends to be improved.
In the composition (x1-1-1), the proportion of the content of the polymer component (a) relative to the total content of all components except the solvent (i.e., the proportion of the content of the polymer component (a) relative to the total mass of the first thermosetting resin film (x1-1) in the first thermosetting resin film (x1-1)) is preferably 5 to 25 mass%, more preferably 5 to 15 mass%, regardless of the kind of the polymer component (a).
(thermosetting component (B))
The thermosetting component (B) is preferably a component having thermosetting properties for thermosetting the first thermosetting resin film (x1-1) to form a hard cured product.
The thermosetting component (B) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
Examples of the thermosetting component (B) include: epoxy thermosetting resins, polyimide resins, unsaturated polyester resins, and the like.
Among these, the thermosetting component (B) is preferably an epoxy thermosetting resin.
Epoxy thermosetting resin
The epoxy thermosetting resin includes an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy thermosetting resin contained in the composition (x1-1-1) and the first thermosetting resin film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
Epoxy resin (B1)
Examples of the epoxy resin (B1) include known epoxy resins, and examples thereof include: polyfunctional epoxy resins, biphenyl compounds, bisphenol a diglycidyl ether and hydrogenated compounds thereof, o-cresol novolac epoxy resins, dicyclopentadiene epoxy resins, biphenyl epoxy resins, bisphenol a epoxy resins, bisphenol F epoxy resins, phenylene skeleton epoxy resins, and other epoxy compounds having two or more functional groups.
The epoxy resin (B1) may be an epoxy resin having an unsaturated hydrocarbon group. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, by using the epoxy resin having an unsaturated hydrocarbon group, for example, the reliability of the package obtained by using the first thermosetting resin film (x1-1) tends to be improved.
Examples of the epoxy resin having an unsaturated hydrocarbon group include: a compound in which a part of the epoxy groups of the polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group.
Examples of the epoxy resin having an unsaturated hydrocarbon group include: a compound having an unsaturated hydrocarbon group directly bonded to an aromatic ring or the like constituting the epoxy resin.
The unsaturated hydrocarbon group is an unsaturated group having polymerizability, and specific examples thereof include: vinyl (vinyl), 2-propenyl (allyl), (meth) acryloyl, (meth) acrylamido and the like, and acryloyl is preferred.
The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000, from the viewpoints of curability of the first thermosetting resin film (x1-1) and strength and heat resistance of a cured product of the first thermosetting resin film (x 1-1).
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1,000g/eq, more preferably 200 to 800 g/eq.
The epoxy resin (B1) may be used alone or in combination of two or more, and when two or more are used in combination, the combination and ratio thereof may be arbitrarily selected.
Heat-curing agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
Examples of the thermosetting agent (B2) include: 1 molecule of a compound having 2 or more functional groups capable of reacting with an epoxy group. Examples of the functional group include: and a group obtained by forming an acid anhydride of a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, or an acid group, and the like, preferably a group obtained by forming an acid anhydride of a phenolic hydroxyl group, an amino group, or an acid group, and more preferably a phenolic hydroxyl group or an amino group.
Examples of the phenolic curing agent having a phenolic hydroxyl group in the thermosetting agent (B2) include: multifunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-type phenol resins, aralkyl phenol resins, and the like.
Examples of the amine-based curing agent having an amino group in the thermosetting agent (B2) include: dicyandiamide (hereinafter, sometimes abbreviated as "DICY") and the like.
The thermosetting agent (B2) may have an unsaturated hydrocarbon group.
Examples of the unsaturated hydrocarbon group-containing thermosetting agent (B2) include: a compound in which a part of the hydroxyl groups of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring of the phenol resin, or the like.
The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group.
The number average molecular weight of the resin component such as the polyfunctional phenol resin, the novolak phenol resin, the dicyclopentadiene phenol resin, and the aralkyl phenol resin in the thermosetting agent (B2) is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000.
The molecular weight of the non-resin component in the thermosetting agent (B2), such as biphenol or dicyandiamide, is not particularly limited, and is preferably 60 to 500, for example.
The heat-curing agent (B2) may be used alone or in combination of two or more, and when two or more are used in combination, the combination and ratio thereof may be arbitrarily selected.
In the composition (x1-1-1) and the first thermosetting resin film (x1-1), the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, and may be any of 5 to 150 parts by mass, 10 to 100 parts by mass, and 15 to 75 parts by mass, relative to 100 parts by mass of the content of the epoxy resin (B1). By setting the content of the thermosetting agent (B2) to the lower limit or more, the curing of the first thermosetting resin film (x1-1) becomes easier. When the content of the thermosetting agent (B2) is not more than the upper limit, the moisture absorption rate of the first thermosetting resin film (x1-1) is reduced, and the reliability of the package obtained using the first thermosetting resin film (x1-1), for example, is further improved.
In the composition (x1-1-1) and the first thermosetting resin film (x1-1), the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is preferably 600 to 1000 parts by mass with respect to 100 parts by mass of the content of the polymer component (a). When the content of the thermosetting component (B) is within such a range, the effect of suppressing the first thermosetting resin film (x1-1) from remaining on the upper portion of the bump, the effect of suppressing the first thermosetting resin film (x1-1) from overflowing, the effect of suppressing the first thermosetting resin film (x1-1) and the shrinkage of the cured product thereof on the bump formation surface, and the effect of improving the filling property of the first thermosetting resin film (x1-1) into the groove portion can be further improved, and a hard cured product can be formed, when the first thermosetting resin film (x1-1) is attached to the bump formation surface of the semiconductor chip production wafer.
Further, from the viewpoint of more remarkably obtaining such effects, the content of the thermosetting component (B) may be appropriately adjusted depending on the kind of the polymer component (a).
For example, when the polymer component (A) is the polyvinyl acetal, the content of the thermosetting component (B) in the composition (x1-1-1) and the first thermosetting resin film (x1-1) is preferably 600 to 1,000 parts by mass, more preferably 650 to 1,000 parts by mass, and particularly preferably 650 to 950 parts by mass, based on 100 parts by mass of the content of the polymer component (A).
(Filler (D))
The above X value can be more easily adjusted by adjusting the amounts of the filler (D) in the composition (X1-1-1) and the first thermosetting resin film (X1-1). Further, by adjusting the amount of the filler (D) in the composition (x1-1-1) and the first thermosetting resin film (x1-1), the thermal expansion coefficient of the cured product of the first thermosetting resin film (x1-1) can be adjusted more easily, and for example, by optimizing the thermal expansion coefficient of the cured product of the first thermosetting resin film (x1-1) with respect to the object to be formed with the cured product, the reliability of the package obtained using the first thermosetting resin film (x1-1) is further improved. Further, by using the first thermosetting resin film (x1-1) containing the filler (D), it is also possible to reduce the moisture absorption rate of the cured product of the first thermosetting resin film (x1-1) or improve the heat release property.
The filler (D) may be any of an organic filler and an inorganic filler, but is preferably an inorganic filler.
Preferred inorganic fillers include, for example: powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, and the like; beads obtained by spheroidizing these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic filler materials; glass fibers, and the like.
Of these, the inorganic filler is preferably silica or alumina.
The filler (D) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the composition (x1-1-1), the proportion of the content of the filler (D) relative to the total content of all the components except the solvent (i.e., the proportion of the content of the filler (D) relative to the total mass of the first thermosetting resin film (x1-1) in the first thermosetting resin film (x1-1)) is preferably 5 to 45 mass%, more preferably 5 to 40 mass%, and still more preferably 5 to 30 mass%. When the above ratio is within such a range, the effect of suppressing the first thermosetting resin film (x1-1) from remaining on the upper portion of the bump, the effect of suppressing the first thermosetting resin film (x1-1) from overflowing, the effect of suppressing the first thermosetting resin film (x1-1) and the shrinkage cavity of the cured product thereof on the bump formation surface, and the effect of improving the filling property of the first thermosetting resin film (x1-1) into the groove portion can be further improved, and the above thermal expansion coefficient can be more easily adjusted, when the first thermosetting resin film (x1-1) is attached to the bump formation surface of the semiconductor chip production wafer.
(additive (I))
By adjusting the kind or amount of the additive (I) in the composition (X1-1-1) and the first thermosetting resin film (X1-1), Gc1 can be adjusted to be appropriate, and the above X value can be adjusted more easily.
Among them, as the preferable additive (I) in view of enabling the value of X to be more easily adjusted, for example: rheology modifiers, surfactants, silicone oils, and the like.
More specifically, examples of the rheology modifier include: polyhydroxycarboxylic acid esters, polycarboxylic acids, polyamide resins, and the like.
Examples of the surfactant include: modified silicones, acrylic polymers, and the like.
Examples of the silicone oil include: aralkyl-modified silicone oil, modified polydimethylsiloxane and the like, and examples of the modifying group include: aralkyl group; polar groups such as hydroxyl groups; and groups having an unsaturated bond such as vinyl and phenyl.
As the additive (I) other than the above, for example: plasticizer, antistatic agent, antioxidant, getter, ultraviolet absorbent, tackifier, etc.
The additive (I) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
The content of the additive (I) in the composition (x1-1-1) and the first thermosetting resin film (x1-1) is not particularly limited, and may be appropriately adjusted depending on the type and purpose thereof.
For example, for the purpose of adjusting the above X value, in the composition (X1-1-1), the proportion of the content of the additive (I) to the total content of all components except the solvent (i.e., the proportion of the content of the additive (I) to the total mass of the first thermosetting resin film (X1-1) in the first thermosetting resin film (X1-1)) is preferably 0.5 to 10 mass%, more preferably 0.5 to 7 mass%, and still more preferably 0.5 to 5 mass%.
(curing Accelerator (C))
The composition (x1-1-1) and the first thermosetting resin film (x1-1) may also contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing rate of the composition (x 1-1-1).
Preferred examples of the curing accelerator (C) include: tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and the like; imidazoles (imidazole in which 1 or more hydrogen atoms are replaced with a group other than a hydrogen atom) such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organophosphines (phosphines in which 1 or more hydrogen atoms are substituted with an organic group) such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenyl radical
Figure BDA0003714954500000231
Tetraphenylboron salts such as tetraphenylboron salt and triphenylphosphine tetraphenylboron salt.
The curing accelerator (C) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
When the curing accelerator (C) is used, the content of the curing accelerator (C) in the composition (x1-1-1) and the first thermosetting resin film (x1-1) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the content of the thermosetting component (B). By setting the content of the curing accelerator (C) to the lower limit or more, the effect of using the curing accelerator (C) can be more remarkably obtained. By setting the content of the curing accelerator (C) to the upper limit or less, for example, the effect of suppressing the occurrence of segregation of the highly polar curing accelerator (C) by moving to the side of the adhesion interface with the adherend in the first thermosetting resin film (x1-1) under high temperature/high humidity conditions is improved, and for example, the reliability of the package obtained by using the first thermosetting resin film (x1-1) is further improved.
(coupling agent (E))
The composition (x1-1-1) and the first thermosetting resin film (x1-1) may also contain a coupling agent (E). By using a component having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (E), the adhesiveness and adhesion of the first thermosetting resin film (x1-1) to the adherend can be further improved. Further, by using the coupling agent (E), the water resistance of the cured product of the first thermosetting resin film (x1-1) can be improved without impairing the heat resistance.
The coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional group of the polymer component (a), the thermosetting component (B), or the like, and more preferably a silane coupling agent.
Preferred examples of the silane coupling agent include: 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxyethyltrimethoxysilane, 3-epoxyethyltrimethoxysilane, 2-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-epoxytrimethoxysilane, 3-glycidyloxyethyltrimethoxysilane, 3-epoxytriethoxysilane, 3-epoxypropyltrimethoxysilane, 3-epoxytriethoxysilane, 3-glycidyloxyethyltrimethoxysilane, 3-epoxypropyltrimethoxysilane, 3-epoxytriethoxysilane, 3-epoxytrimethoxysilane, 3-epoxypropyltrimethoxysilane, 3-epoxytrimethoxysilane, 3-epoxypropyl-epoxysilane, 2-epoxypropyl-2, and 2-epoxypropyl-hydroxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane and the like.
The coupling agent (E) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
When the coupling agent (E) is used, the content of the coupling agent (E) in the composition (x1-1-1) and the first thermosetting resin film (x1-1) is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total content of the polymer component (A) and the thermosetting component (B). By setting the content of the coupling agent (E) to the lower limit or more, effects of using the coupling agent (E), such as improvement in dispersibility of the filler (D) in the resin and improvement in adhesiveness of the first thermosetting resin film (x1-1) to the object to be adhered, can be more remarkably obtained. By setting the content of the coupling agent (E) to the upper limit or less, the generation of outgas can be further suppressed.
(crosslinking agent (F))
When a resin having a functional group such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, or isocyanate group, which is capable of bonding to another compound, is used as the polymer component (a), the composition (X1-1-1) and the first thermosetting resin film (X1-1) may contain a crosslinking agent (F). The crosslinking agent (F) is a component for crosslinking the functional group in the polymer component (a) by bonding with another compound, and the initial adhesion and cohesive force of the first thermosetting resin film (x1-1) can be adjusted by crosslinking in this way.
Examples of the crosslinking agent (F) include: an organic polyisocyanate compound, an organic polyamine compound, a metal chelate-based crosslinking agent (a crosslinking agent having a metal chelate structure), an aziridine-based crosslinking agent (a crosslinking agent having an aziridine group), and the like.
Examples of the organic polyisocyanate compound include: an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound (hereinafter, these compounds may be collectively referred to simply as "aromatic polyisocyanate compound or the like"); trimers, isocyanurates and adducts of the above aromatic polyisocyanate compounds and the like; and isocyanate-terminated urethane prepolymers obtained by reacting the aromatic polyisocyanate compounds and the like with polyol compounds. The "adduct" means a reaction product of the aromatic polyisocyanate compound, the aliphatic polyisocyanate compound or the alicyclic polyisocyanate compound with a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. Examples of the adduct include xylylene diisocyanate adducts of trimethylolpropane, which will be described later. The "isocyanate-terminated urethane prepolymer" refers to a prepolymer having a urethane bond and an isocyanate group at the terminal of the molecule.
More specifically, the organic polyisocyanate compound includes, for example: 2, 4-toluene diisocyanate; 2, 6-toluene diisocyanate; 1, 3-xylylene diisocyanate; 1, 4-xylylene diisocyanate; diphenylmethane-4, 4' -diisocyanate; diphenylmethane-2, 4' -diisocyanate; 3-methyl diphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4, 4' -diisocyanate; dicyclohexylmethane-2, 4' -diisocyanate; a compound obtained by adding one or more of tolylene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate to all or part of the hydroxyl groups of a polyhydric alcohol such as trimethylolpropane; lysine diisocyanate, and the like.
Examples of the organic polyamine compound include: n, N ' -diphenylmethane-4, 4 ' -bis (1-aziridinecarboxamide), trimethylolpropane-tris- β -aziridinylpropionate, tetramethylolmethane-tris- β -aziridinylpropionate, N ' -toluene-2, 4-bis (1-aziridinecarboxamide) triethylenemelamine, and the like.
When an organic polyisocyanate compound is used as the crosslinking agent (F), a hydroxyl group-containing polymer is preferably used as the polymer component (a). When the crosslinking agent (F) has an isocyanate group and the polymer component (a) has a hydroxyl group, a crosslinked structure can be easily introduced into the first thermosetting resin film (x1-1) by reacting the crosslinking agent (F) with the polymer component (a).
The crosslinking agent (F) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the crosslinking agent (F) is used, the content of the crosslinking agent (F) in the composition (x1-1-1) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the content of the polymer component (A). By setting the content of the crosslinking agent (F) to the lower limit or more, the effect of using the crosslinking agent (F) can be more remarkably obtained. When the content of the crosslinking agent (F) is not more than the upper limit value, the excessive use of the crosslinking agent (F) can be suppressed.
(energy ray-curable resin (G))
The composition (x1-1-1) and the first thermosetting resin film (x1-1) may contain an energy ray-curable resin (G).
By containing the energy ray-curable resin (G) in the first thermosetting resin film (x1-1), the characteristics can be changed by irradiation with an energy ray.
The energy ray-curable resin (G) is a resin obtained by polymerizing (curing) an energy ray-curable compound. Examples of the energy ray-curable compound include compounds having at least 1 polymerizable double bond in the molecule, and acrylate compounds having a (meth) acryloyl group are preferable.
Examples of the acrylate-based compound include: (meth) acrylates having a chain-like aliphatic skeleton such as trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol di (meth) acrylate; cyclic aliphatic skeleton-containing (meth) acrylates such as dicyclopentyl di (meth) acrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate; an oligoester (meth) acrylate; a urethane (meth) acrylate oligomer; epoxy-modified (meth) acrylates; polyether (meth) acrylates other than the polyalkylene glycol (meth) acrylates; itaconic acid oligomers, and the like.
The weight average molecular weight of the energy ray-curable compound is preferably 100 to 30,000, more preferably 300 to 10,000.
The energy ray-curable compound used for the polymerization may be used alone or in combination of two or more. When two or more kinds of the energy ray-curable compounds are used for the polymerization, the combination and ratio of the two or more kinds can be arbitrarily selected.
When the energy ray-curable resin (G) is used, the content of the energy ray-curable resin (G) is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and still more preferably 10 to 85% by mass, based on the total amount of the active ingredients of the composition (x 1-1-1).
(photopolymerization initiator (H))
In the case where the composition (x1-1-1) and the first thermosetting resin film (x1-1) contain the energy ray-curable resin (G), a photopolymerization initiator (H) may be contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) in order to efficiently progress the polymerization reaction of the energy ray-curable resin (G).
Examples of the photopolymerization initiator (H) include: benzophenone, acetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ether, 2, 4-diethylthioxanthone, 1-hydroxycyclohexylphenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzil, bibenzyl, butanedione, 1, 2-diphenylmethane, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2-chloroanthraquinone, and the like.
The photopolymerization initiator (H) may be used alone or in combination of two or more. When two or more photopolymerization initiators (H) are used, the combination and ratio thereof can be selected arbitrarily.
In the composition (x1-1-1), the content of the photopolymerization initiator (H) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 2 to 5 parts by mass, relative to 100 parts by mass of the content of the energy ray-curable resin (G).
(other Components)
The composition (x1-1-1) and the first thermosetting resin film (x1-1) may contain other components not included in any of the polymer component (a), the thermosetting component (B), the curing accelerator (C), the filler (D), the coupling agent (E), the crosslinking agent (F), the energy ray-curable resin (G), the photopolymerization initiator (H), and the additive (I) as long as the effects of the present invention are not impaired.
The other components contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
The content of the other components in the composition (x1-1-1) and the first thermosetting resin film (x1-1) is not particularly limited, and may be appropriately selected according to the purpose.
(solvent)
The composition (x1-1-1) preferably further contains a solvent. The handling property of the solvent-containing composition (x1-1-1) was improved.
The solvent is not particularly limited, and preferable examples thereof include: hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The solvent contained in the composition (x1-1-1) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
As a more preferable solvent among the solvents contained in the composition (x1-1-1), methyl ethyl ketone and the like can be mentioned from the viewpoint of enabling the components contained in the composition (x1-1-1) to be more uniformly mixed.
The content of the solvent in the composition (x1-1-1) is not particularly limited, and may be appropriately selected depending on the kind of components other than the solvent.
< method for producing first composition for Forming thermosetting resin film (x1-1-1) >
The first thermosetting resin film-forming composition (x1-1-1) can be obtained by blending the components constituting the composition.
The order of addition in the case of dispensing the respective components is not particularly limited, and two or more components may be added simultaneously.
The method for mixing the components at the time of compounding is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer, a paddle, or the like; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves, and the like.
The temperature and time for adding and mixing the components are not particularly limited as long as the components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ℃.
< first energy ray-curable resin film (x1-2) >
The curing conditions for curing the first energy ray-curable resin film (x1-2) to form the first cured resin film (r1) as a cured product thereof are not particularly limited as long as the cured product has a degree of curing sufficient to exert its function, and may be appropriately selected depending on the type of the first energy ray-curable resin film (x1-2), the use of the cured product, and the like.
For example, when the first energy ray-curable resin film (x1-2) is cured, the illuminance of the energy ray is preferably 180 to 280mW/cm 2 . The amount of the energy ray is preferably 450 to 1000mJ/cm during curing 2 。
< first energy ray-curable resin film-Forming composition (x1-2-1) >
Examples of the first energy ray-curable resin film-forming composition (x1-2-1) include: a first energy ray-curable resin film-forming composition (x1-2-1) (in the present specification, it may be simply referred to as "composition (x 1-2-1)") containing an energy ray-curable component (a), a filler and an additive.
(energy ray-curable component (a))
The energy ray-curable component (a) is a component that is cured by irradiation with an energy ray, and is also a component for imparting film formability, flexibility, and the like to the first energy ray-curable resin film (x 1-2).
The energy ray-curable component (a) is preferably uncured, preferably has adhesiveness, and more preferably is uncured and has adhesiveness.
Examples of the energy ray-curable component (a) include: a polymer (a1) having an energy ray-curable group and a weight-average molecular weight of 80,000 to 2,000,000, and a compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80,000. The polymer (a1) may be a polymer at least a part of which has been crosslinked with a crosslinking agent, or may be a polymer that has not been crosslinked.
A polymer (a1) having an energy ray-curable group and a weight-average molecular weight of 80,000 to 2,000,000
Examples of the polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000 include: an acrylic resin (a1-1) obtained by polymerizing an acrylic polymer (a11) having a functional group capable of reacting with a group contained in another compound and an energy ray-curable compound (a12) having a group capable of reacting with the functional group and an energy ray-curable group such as an energy ray-curable double bond.
Examples of the functional group that can react with a group of another compound include: a hydroxyl group, a carboxyl group, an amino group, a substituted amino group (a group in which 1 or 2 hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom), an epoxy group, and the like. Among them, from the viewpoint of preventing corrosion of circuits of semiconductor wafers, semiconductor chips, and the like, it is preferable that the functional group is a group other than a carboxyl group.
Among these, the functional group is preferably a hydroxyl group.
Acrylic Polymer having functional group (a11)
Examples of the acrylic polymer (a11) having the functional group include: the polymer obtained by copolymerizing the acrylic monomer having the functional group and the acrylic monomer having no functional group may be a polymer obtained by further copolymerizing a monomer other than the acrylic monomer (non-acrylic monomer) in addition to these monomers.
The acrylic polymer (a11) may be a random copolymer or a block copolymer.
As the acrylic monomer having the above functional group, for example: hydroxyl-containing monomers, carboxyl-containing monomers, amino-containing monomers, substituted amino-containing monomers, epoxy-containing monomers and the like.
Examples of the hydroxyl group-containing monomer include: hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; and non (meth) acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (unsaturated alcohols having no (meth) acryloyl skeleton).
Examples of the carboxyl group-containing monomer include: ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; anhydrides of the above ethylenically unsaturated dicarboxylic acids; and carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate.
The acrylic monomer having the functional group is preferably a hydroxyl group-containing monomer or a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.
The acrylic monomer having the functional group constituting the acrylic polymer (a11) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
Examples of the acrylic monomer having no functional group include: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, myristyl (meth) acrylate, And alkyl (meth) acrylates having a chain structure in which the alkyl group constituting the alkyl ester has 1 to 18 carbon atoms, such as pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearyl (meth) acrylate).
As the acrylic monomer having no functional group, for example: alkoxyalkyl group-containing (meth) acrylates such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate; aromatic group-containing (meth) acrylates including aryl (meth) acrylates such as phenyl (meth) acrylate; non-crosslinkable (meth) acrylamide and derivatives thereof; and (meth) acrylic esters having a non-crosslinkable tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate.
The acrylic monomer having no functional group constituting the acrylic polymer (a11) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
Examples of the non-acrylic monomer include: olefins such as ethylene and norbornene; vinyl acetate; styrene, and the like.
The non-acrylic monomer constituting the acrylic polymer (a11) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
In the acrylic polymer (a11), the proportion (content) of the structural unit derived from the acrylic monomer having the functional group is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass, relative to the total amount of the structural units constituting the polymer. When the ratio is in such a range, the content of the energy ray-curable group in the acrylic resin (a1-1) obtained by copolymerizing the acrylic polymer (a11) and the energy ray-curable compound (a12) can be easily adjusted to a preferable range of the degree of curing of the cured product of the first energy ray-curable resin film (x 1-2).
The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
In the composition (x1-2-1), the proportion of the content of the acrylic resin (a1-1) relative to the total content of components other than the solvent (i.e., the proportion of the content of the acrylic resin (a1-1) in the first energy-ray curable resin film (x1-2) relative to the total mass of the film) is preferably 1 to 40 mass%, more preferably 2 to 30 mass%, and particularly preferably 3 to 20 mass%.
Energy ray-curable compound (a12)
The energy ray-curable compound (a12) is preferably a compound having one or more selected from the group consisting of an isocyanate group, an epoxy group and a carboxyl group as a group capable of reacting with the functional group of the acrylic polymer (a11), and more preferably a compound having an isocyanate group as the group. When the energy ray-curable compound (a12) has an isocyanate group as the above group, for example, the isocyanate group is likely to react with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the above functional group.
The energy ray-curable compound (a12) preferably has 1 to 5, more preferably 1 to 2 energy ray-curable groups in 1 molecule.
Examples of the energy ray-curable compound (a12) include:
2-methacryloyloxyethyl isocyanate, m-isopropenyl- α, α -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1- (bisacryloxymethyl) ethyl isocyanate;
a diisocyanate compound or a polyisocyanate compound, and a acryloyl monoisocyanate compound obtained by reacting hydroxyethyl (meth) acrylate;
and an acryloyl group monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with a polyol compound and hydroxyethyl (meth) acrylate.
Among these, the energy ray-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.
The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic resin (a1-1), the ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the ratio of the above content is within such a range, the adhesive strength of the cured product of the energy ray-curable resin film (x1-2) becomes higher. When the energy ray-curable compound (a12) is a monofunctional compound (having 1 group in the molecule), the upper limit of the content ratio is 100 mol%, but when the energy ray-curable compound (a12) is a polyfunctional compound (having 2 or more groups in the molecule), the upper limit of the content ratio may exceed 100 mol%.
The weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, more preferably 300,000 to 1,500,000.
When the polymer (a1) is a polymer at least a part of which is crosslinked by a crosslinking agent, the polymer (a1) may be a polymer obtained by polymerizing a monomer having a group reactive with the crosslinking agent, which is not any of the monomers described above as monomers constituting the acrylic polymer (a11), and crosslinking the polymer by a group reactive with the crosslinking agent, or a polymer obtained by crosslinking the polymer by a group reactive with the functional group derived from the energy ray-curable compound (a 12).
The polymer (a1) contained in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
The energy ray-curable group in the compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80,000 includes a group containing an energy ray-curable double bond, and preferable examples thereof include a (meth) acryloyl group and a vinyl group.
The compound (a2) is not particularly limited as long as it satisfies the above conditions, and examples thereof include: a low molecular weight compound having an energy ray-curable group, an epoxy resin having an energy ray-curable group, a phenol resin having an energy ray-curable group, and the like.
Among the compounds (a2), examples of the low molecular weight compound having an energy ray-curable group include polyfunctional monomers and oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
Examples of the acrylic ester compounds include:
2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloyloxypolyethoxy) phenyl ] propane, ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloyloxydiethoxy) phenyl ] propane, 9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl ] fluorene, 2-bis [4- ((meth) acryloyloxypolypropoxy) phenyl ] propane, tricyclodecanedimethanol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, poly (ethylene glycol di (meth) acrylate), poly (propylene glycol di (meth) acrylate, poly (ethylene glycol di (meth) acrylate, poly (ethylene glycol, poly (meth) acrylate, bis (meth) acrylate, poly (ethylene glycol, poly (meth) acrylate, poly (ethylene glycol, poly (meth) acrylate, poly (meth, Difunctional (meth) acrylates such as 1, 9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2-bis [4- ((meth) acryloyloxyethoxy) phenyl ] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, and 2-hydroxy-1, 3-di (meth) acryloyloxypropyl;
polyfunctional (meth) acrylates such as tris (2- (meth) acryloyloxyethyl) isocyanurate, epsilon-caprolactone-modified tris- (2- (meth) acryloyloxyethyl) isocyanurate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, and dipentaerythritol hexa (meth) acrylate;
and polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.
As the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group in the above compound (a2), for example, those described in paragraph 0043 and the like of "japanese patent application laid-open No. 2013-194102" can be used. Such a resin is also a resin constituting a thermosetting component described later, but is treated as the above-mentioned compound (a2) in the present invention.
The weight average molecular weight of the compound (a2) is preferably 100 to 30,000, more preferably 300 to 10,000.
The compound (a2) contained in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
(Polymer (b) having no energy ray-curable group)
When the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) contain the compound (a2) as the energy ray-curable component (a), it is preferable that the composition further contains a polymer (b) having no energy ray-curable group.
The polymer (b) may be a polymer at least a part of which is crosslinked with a crosslinking agent, or may be a polymer that is not crosslinked.
Examples of the polymer (b) having no energy ray-curable group include: acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, acrylic urethane resins, and the like.
Among these polymers, the polymer (b) is preferably an acrylic polymer (hereinafter, may be abbreviated as "acrylic polymer (b-1)").
The acrylic polymer (b-1) may be a known one, and may be, for example, a homopolymer of one acrylic monomer, a copolymer of two or more acrylic monomers, or a copolymer of one or more acrylic monomers and one or more monomers other than the acrylic monomers (non-acrylic monomers).
Examples of the acrylic monomer constituting the acrylic polymer (b-1) include: alkyl (meth) acrylates, (meth) acrylates having a cyclic skeleton, glycidyl group-containing (meth) acrylates, hydroxyl group-containing (meth) acrylates, substituted amino group-containing (meth) acrylates, and the like. Here, the "substituted amino group" is as described above.
Examples of the alkyl (meth) acrylate include those similar to the acrylic monomers (alkyl (meth) acrylates in which the alkyl group constituting the alkyl ester has a chain structure of 1 to 18 carbon atoms, etc.) constituting the acrylic polymer (a11) described above and having no functional group.
Examples of the (meth) acrylate having a cyclic skeleton include:
cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
aralkyl (meth) acrylates such as benzyl (meth) acrylate;
cycloalkenyl (meth) acrylates such as dicyclopentenyl (meth) acrylate;
and cycloalkenyloxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate.
Examples of the glycidyl group-containing (meth) acrylate include: glycidyl (meth) acrylate, and the like.
Examples of the hydroxyl group-containing (meth) acrylate include: hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
Examples of the substituted amino group-containing (meth) acrylate include: n-methylaminoethyl (meth) acrylate, and the like.
Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include: olefins such as ethylene and norbornene; vinyl acetate; styrene, and the like.
Examples of the polymer (b) having no energy ray-curable group, at least a part of which is crosslinked by a crosslinking agent, include: a polymer obtained by reacting the reactive functional group in the polymer (b) with a crosslinking agent.
The reactive functional group may be appropriately selected depending on the kind of the crosslinking agent, and the like, and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, the reactive functional group includes a hydroxyl group, a carboxyl group, an amino group, and the like, and among these functional groups, a hydroxyl group having high reactivity with an isocyanate group is preferable. When the crosslinking agent is an epoxy compound, examples of the reactive functional group include a carboxyl group, an amino group, and an amide group, and among these functional groups, a carboxyl group having high reactivity with an epoxy group is preferable. In view of preventing corrosion of circuits of semiconductor wafers and semiconductor chips, the reactive functional group is preferably a group other than a carboxyl group.
Examples of the polymer (b) having no energy ray-curable group and having the reactive functional group include polymers obtained by polymerizing monomers having at least the reactive functional group. In the case of the acrylic polymer (b-1), a monomer having the reactive functional group may be used as either or both of the acrylic monomer and the non-acrylic monomer described above with reference to the monomer constituting the polymer. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include, for example, a polymer obtained by polymerizing a hydroxyl group-containing (meth) acrylate, and in addition to the above, a polymer obtained by polymerizing a monomer in which 1 or 2 or more hydrogen atoms in the above-mentioned acrylic monomer or non-acrylic monomer are substituted with the above-mentioned reactive functional group.
In the polymer (b) having a reactive functional group, the proportion (content) of the amount of the structural unit derived from the monomer having a reactive functional group to the total amount of the structural units constituting the polymer is preferably 1 to 20% by mass, more preferably 2 to 10% by mass. By setting the above ratio within such a range, the degree of crosslinking in the above polymer (b) can be brought into a more preferable range.
The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000, from the viewpoint of further improving the film-forming properties of the composition (x 1-2-1).
The number of the polymers (b) having no energy ray-curable group contained in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) may be one or two or more, and when two or more, the combination and ratio thereof may be arbitrarily selected.
The composition (x1-2-1) may be a composition containing either one or both of the polymer (a1) and the compound (a 2). Among them, in the case where the composition (x1-2-1) contains the compound (a2), it is preferable that the composition further contains a polymer (b) having no energy ray-curable group, and in this case, it is preferable that the composition further contains the polymer (a 1). The composition (x1-2-1) may contain the polymer (a1) and the polymer (b) having no energy ray-curable group in addition to the compound (a 2).
When the composition (x1-2-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group, the content of the compound (a2) in the composition (x1-2-1) is preferably 10 to 400 parts by mass, more preferably 30 to 350 parts by mass, based on 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group.
In the composition (x1-2-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (i.e., the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total mass of the film in the first energy ray-curable resin film (x 1-2)) is preferably 5 to 90 mass%, more preferably 10 to 80 mass%, and particularly preferably 20 to 70 mass%. When the ratio is in such a range, the energy ray curability of the first energy ray-curable resin film (x1-2) is further improved.
(Filler)
The above X value can be more easily adjusted by adjusting the amounts of the filler in the composition (X1-2-1) and the first energy ray-curable resin film (X1-2). Further, by adjusting the amount of the filler in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2), the thermal expansion coefficient of the cured product of the first energy ray-curable resin film (x1-2) can be adjusted more easily, and for example, by optimizing the thermal expansion coefficient of the cured product of the first energy ray-curable resin film (x1-2) with respect to the object to be protected film, the reliability of the package obtained using the first energy ray-curable resin film (x1-2) is further improved. Further, by using the first energy ray-curable resin film (x1-2) containing a filler, the moisture absorption rate of the cured product of the first energy ray-curable resin film (x1-2) can be reduced, or the heat radiation property can be improved.
The filler contained in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) is the same as the filler (D) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) described above.
The form of the filler contained in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) may be the same as the form of the filler (D) contained in the composition (x1-1-1) and the first thermosetting resin film (x 1-1).
The filler contained in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
In the composition (x1-2-1), the proportion of the content of the filler relative to the total content of all the components except the solvent (i.e., the proportion of the content of the filler in the first energy ray-curable resin film (x1-2) relative to the total mass of the first energy ray-curable resin film (x 1-2)) may be, for example, 5 to 45 mass%. When the first energy ray-curable resin film (x1-2) is bonded to the bump formation surface of the semiconductor chip production wafer in such a range, the effect of suppressing the first energy ray-curable resin film (x1-2) from remaining on the upper portion of the bump, the effect of suppressing the first energy ray-curable resin film (x1-2) from overflowing, the effect of suppressing the first energy ray-curable resin film (x1-2) on the bump formation surface and shrinkage cavities of the cured product thereof, and the effect of improving the filling ability of the first energy ray-curable resin film (x1-2) into the grooves are further improved, and the thermal expansion coefficient can be more easily adjusted.
(additives)
The X value can be more easily adjusted by adjusting the kind or amount of the additive in the composition (X1-2-1) and the first energy ray-curable resin film (X1-2).
The additives contained in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) are the same as the additive (I) contained in the composition (x1-1-1) and the first thermosetting resin film (x1-1) described above.
For example, the value of X can be more easily adjusted, and preferable additives include rheology control agents, surfactants, silicone oils, and the like.
The form of the additive contained in the composition (X1-2-1) and the first energy ray-curable resin film (X1-2) may be the same as the form of the additive (I) contained in the composition (X1-1-1) and the first thermosetting resin film (X1-1).
The additive contained in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
The content of the additive in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) is not particularly limited, and may be appropriately adjusted depending on the type and purpose thereof.
For example, in the case where the above X value is to be adjusted, the ratio of the content of the additive to the total content of all the components except the solvent in the composition (X1-2-1) (i.e., the ratio of the content of the additive in the first energy ray-curable resin film (X1-2) to the total mass of the first energy ray-curable resin film (X1-2)) may be, for example, 0.5 to 10 mass%.
(other Components)
The composition (x1-2-1) and the first energy ray-curable resin film (x1-2) may contain other components not included in the energy ray-curable component (a), the filler and the additive, within a range not to impair the effects of the present invention.
Examples of the other components include: thermosetting component, photopolymerization initiator, coupling agent, crosslinking agent, etc. For example, by using the composition (x1-2-1) containing the energy ray-curable component (a) and the thermosetting component, the adhesion of the first energy ray-curable resin film (x1-2) to an adherend can be improved by heating, and the strength of the cured product of the first energy ray-curable resin film (x1-2) is also improved.
Examples of the thermosetting component, photopolymerization initiator, coupling agent and crosslinking agent in the composition (x1-2-1) include those similar to the thermosetting component (B), photopolymerization initiator, coupling agent (E) and crosslinking agent (F) in the composition (x1-1-1), respectively.
The other components contained in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) may be only one type, or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
The content of the other components in the composition (x1-2-1) and the first energy ray-curable resin film (x1-2) is not particularly limited, and may be appropriately selected according to the purpose.
(solvent)
The composition (x1-2-1) preferably further contains a solvent. The handling property of the solvent-containing composition (x1-2-1) became good.
Examples of the solvent contained in the composition (x1-2-1) include the same solvents as those contained in the composition (x1-1-1) described above.
The solvent contained in the composition (x1-2-1) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
The content of the solvent in the composition (x1-2-1) is not particularly limited, and may be appropriately selected depending on the kind of components other than the solvent, for example.
< first method for producing energy ray-curable resin film-forming composition >
The first energy ray-curable resin film-forming composition (x1-2-1) can be obtained by blending the components constituting the composition.
The first energy ray-curable resin film-forming composition (x1-2-1) can be produced by the same method as in the case of the first thermosetting resin film-forming composition (x1-1-1) described above, except that, for example, the kinds of components to be blended are different.
[ first composite sheet (. alpha.1) ]
The first curable resin film (x1) can be laminated with the first support sheet (Y1) to form the first composite sheet (α 1), as described above.
Fig. 3 shows an example of the structure of the first composite sheet (α 1).
The first composite sheet (α 1) includes a layer (X1) of a first curable resin (X1) on one surface of a first support sheet (Y1) as in the first composite sheet (α 1) shown in fig. 3. By providing the layer (X1) of the first curable resin (X1) on one surface of the first support sheet (Y1), the layer (X1) of the first curable resin (X1) can be stably supported and protected when the layer (X1) of the first curable resin (X1) is transported or the layer (X1) of the first curable resin (X1) is transported in a process for producing a product package.
Specific configurations of the first composite sheet (α 1) are shown in fig. 4 to 6, for example.
The first composite sheet (α 1) is, as with the first composite sheet (α 1a) shown in fig. 4, a first support sheet (Y1) serving as a base material 51 and having a layer (X1) of a first curable resin (X1) on one surface of the base material 51.
As in the first composite sheet (α 1b) shown in fig. 5, the first support sheet (Y1) may be a pressure-sensitive adhesive sheet in which the substrate 51 and the pressure-sensitive adhesive layer 61 are laminated, and the pressure-sensitive adhesive layer 61 of the pressure-sensitive adhesive sheet may be bonded to the layer (X1) of the first curable resin (X1).
In the first composite sheet (α 1), as in the first composite sheet (α 1c) shown in fig. 6, the first support sheet (Y1) may be an adhesive sheet in which the substrate 51, the intermediate layer 71, and the adhesive layer 61 are laminated in this order, and the adhesive layer 61 of the adhesive sheet may be bonded to the layer (X1) of the first curable resin (X1). A pressure-sensitive adhesive sheet in which the substrate 51, the intermediate layer 71, and the pressure-sensitive adhesive layer 61 are laminated in this order can be suitably used as a back-grinding tape. That is, since the first composite sheet (α 1c) shown in fig. 6 has a back-grinding tape as the first support sheet (Y1), it can be suitably used when the layer (X1) of the first curable resin (X1) of the first composite sheet (α 1c) is bonded to the bump formation surface of the wafer for semiconductor chip production, and then the back surface of the wafer for semiconductor chip production is ground and thinned.
The first curable resin (x1) and the first support sheet (Y1) used for the first composite sheet (α 1) will be described below.
< first supporting sheet (Y1) >
The first support sheet (Y1) functions as a support for supporting the first curable resin (x 1).
The first support sheet (Y1) may be composed of only the base material 51 as shown in fig. 4, may be a laminate of the base material 51 and the pressure-sensitive adhesive layer 61 as shown in fig. 5, or may be a laminate of the base material 51, the intermediate layer 71, and the pressure-sensitive adhesive layer 61 stacked in this order as shown in fig. 6. A laminate in which the base material 51, the intermediate layer 71, and the adhesive layer 61 are laminated in this order is suitably used as the back grinding sheet (b-BG).
The substrate of the first support sheet (Y1), and the adhesive layer and the intermediate layer that the first support sheet (Y1) may optionally have will be described below.
(substrate)
The substrate is in the form of a sheet or a film, and examples of the constituent material include various resins described below.
Examples of the resin constituting the base material include: polyethylenes such as Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), and High Density Polyethylene (HDPE); polyolefins other than polyethylene, such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resins; ethylene copolymers (copolymers obtained using ethylene as a monomer) such as ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid ester copolymers, and ethylene-norbornene copolymers; vinyl chloride-based resins (resins obtained by using vinyl chloride as a monomer) such as polyvinyl chloride and vinyl chloride copolymers; polystyrene; a polycycloolefin; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene 2, 6-naphthalate, and wholly aromatic polyesters having aromatic ring-type groups in all structural units; copolymers of two or more of the above polyesters; poly (meth) acrylates; a polyurethane; a polyurethane acrylate; a polyimide; a polyamide; a polycarbonate; a fluororesin; a polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfones; polyether ketones, and the like.
Further, as the resin constituting the base material, for example, a polymer alloy such as a mixture of the above polyester and a resin other than the polyester can be cited. In the polymer alloy of the above polyester and the resin other than the polyester, it is preferable that the amount of the resin other than the polyester is smaller.
Further, examples of the resin constituting the base material include: a crosslinked resin obtained by crosslinking one or two or more of the above resins exemplified so far; one or two or more kinds of modified resins such as ionomers among the above resins exemplified so far are used.
The resin constituting the base material may be used alone or in combination of two or more. When two or more kinds of resins are used as the base material, the combination and ratio of the two or more kinds of resins can be arbitrarily selected.
The substrate may be a single layer (single layer) or a multilayer of two or more layers. When the substrate is a multilayer, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.
The thickness of the substrate is preferably 5 to 1,000 μm, more preferably 10 to 500. mu.m, still more preferably 15 to 300. mu.m, and yet more preferably 20 to 150. mu.m.
Here, the "thickness of the substrate" refers to the thickness of the entire substrate, and for example, the thickness of the substrate composed of a plurality of layers refers to the total thickness of all layers constituting the substrate.
The base material is preferably a material having high thickness accuracy, that is, a material in which variation in thickness is suppressed without depending on the location. Among the above-mentioned constituent materials, as a material having high thickness accuracy which can be used for constituting such a base material, for example: polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymers, and the like.
The base material may contain known various additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softening agent (plasticizer), in addition to the main constituent materials such as the above-mentioned resin.
The substrate may be transparent or opaque, may be colored depending on the purpose, or may be vapor-deposited with other layers. When the first curable resin film (x1) is the first energy ray-curable resin film (x1-2) and when the adhesive layer is an energy ray-curable adhesive layer, the substrate is preferably a material that transmits energy rays.
The substrate can be manufactured by a known method. For example, the resin-containing substrate can be produced by molding a resin composition containing the resin.
(adhesive layer)
The adhesive layer is in the form of a sheet or film and contains an adhesive.
Examples of the binder include: an adhesive resin such as an acrylic resin (an adhesive agent formed of a resin having a (meth) acryloyl group), a urethane resin (an adhesive agent formed of a resin having a urethane bond), a rubber resin (an adhesive agent formed of a resin having a rubber structure), a silicone resin (an adhesive agent formed of a resin having a siloxane bond), an epoxy resin (an adhesive agent formed of a resin having an epoxy group), polyvinyl ether, or polycarbonate. Among these, acrylic resins are preferable.
In the present invention, the "adhesive resin" is a concept including both a resin having adhesive properties and a resin having adhesive properties, and includes, for example, not only a case where the resin itself has adhesive properties, but also a resin exhibiting adhesive properties by being used in combination with other components such as an additive, a resin exhibiting adhesive properties by the presence of a trigger (trigger) such as heat or water, and the like.
The adhesive layer may be a single layer (single layer) or may be a multilayer of two or more layers. When the pressure-sensitive adhesive layer is a multilayer, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.
The thickness of the pressure-sensitive adhesive layer is preferably 1 to 1000. mu.m, more preferably 5 to 500. mu.m, and still more preferably 10 to 100. mu.m. Here, the "thickness of the pressure-sensitive adhesive layer" refers to the thickness of the entire pressure-sensitive adhesive layer, and for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers refers to the total thickness of all the layers constituting the pressure-sensitive adhesive layer.
The adhesive layer may be a layer formed using an energy ray-curable adhesive or a layer formed using a non-energy ray-curable adhesive. The physical properties of the pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive before and after curing can be easily adjusted.
(intermediate layer)
The intermediate layer is in the form of a sheet or a film, and the material of the intermediate layer is not particularly limited as long as it is appropriately selected according to the purpose. For example, in the case where the purpose is to suppress the deformation of the first cured resin film (r1) due to the shape of the bumps present on the semiconductor surface being reflected by the protective film covering the semiconductor surface, a urethane (meth) acrylate or the like is mentioned as a preferable constituent material of the intermediate layer from the viewpoint of high irregularity following property and further improvement in the adhesion of the intermediate layer.
The intermediate layer may be only one layer (single layer) or may be a multilayer of two or more layers. When the intermediate layer is a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited.
The thickness of the intermediate layer can be appropriately adjusted depending on the height of the bump on the semiconductor surface to be protected, but is preferably 50 to 600 μm, more preferably 70 to 500 μm, and even more preferably 80 to 400 μm, from the viewpoint of easily absorbing the effect on a bump having a high height. Here, the "thickness of the intermediate layer" refers to the thickness of the entire intermediate layer, and for example, the thickness of the intermediate layer composed of a plurality of layers refers to the total thickness of all the layers constituting the intermediate layer.
Next, a method for manufacturing the first composite sheet (α 1) will be described.
[ method for producing first composite sheet (. alpha.1) ]
The first composite sheet (α 1) can be produced by sequentially laminating the layers so as to have a corresponding positional relationship.
For example, in the case of laminating an adhesive layer or an intermediate layer on a substrate in the production of the first support sheet (Y1), the adhesive layer or the intermediate layer may be laminated by applying an adhesive composition or an intermediate layer-forming composition on the substrate, and drying or irradiating energy rays as necessary.
Examples of the coating method include: spin coating, spray coating, bar coating, knife coating, roll coating, knife coating, blade coating, die coating, gravure coating, and the like.
On the other hand, for example, in the case where the first curable resin (X1) is further laminated on the adhesive layer already laminated on the substrate, the layer (X1) of the first curable resin (X1) can be directly formed by applying the thermosetting resin composition (X1-1-1) or the energy ray curable resin composition (X1-2-1) on the adhesive layer.
Similarly, in the case where an adhesive layer is further laminated on an intermediate layer already laminated on the substrate, the adhesive layer may be directly formed by applying an adhesive composition on the intermediate layer.
In this way, when a laminate structure of two continuous layers is formed using an arbitrary composition, a layer formed of the composition may be further coated with the composition to form a new layer. Among these, it is preferable to form a continuous two-layer laminated structure by forming a later laminated layer of the two layers on a separate release film using the composition, and then bonding an exposed surface of the formed layer on the side opposite to the side in contact with the release film to an exposed surface of the other layer formed. In this case, the composition is preferably applied to the release-treated surface of the release film. The release film may be removed as necessary after the formation of the laminated structure.
[ second composite sheet (. alpha.2) ]
The second composite sheet (α 2) is not particularly limited as long as it can form a protective film on the back surface of the semiconductor wafer, and for example, the same configuration as the first composite sheet (α 1) can be employed.
Therefore, the second curable resin film (x2) included in the second composite sheet (α 2) can be made of the same material and have the same configuration as the first curable resin film (x 1).
Since the back surface of the semiconductor wafer is generally smooth without bumps or grooves, the second curable resin film (x2) is not required to satisfy the condition (I) of the first curable resin film (x 1). Therefore, the value of X in the second curable resin film (X2) may be 18 or less, or 10,000 or more.
(colorant (J))
Here, from the viewpoints of improving visibility of printed characters formed by laser marking, making grinding marks on the back surface of the semiconductor chip less likely to be observed, and improving design properties of the semiconductor chip, and the like, the second curable resin film (x2) and the second curable resin film-forming composition for forming the second curable resin film (x2) preferably contain the colorant (J).
Examples of the colorant (J) include: known colorants such as inorganic pigments, organic pigments, and organic dyes.
Examples of the organic pigments and organic dyes include: ammonium dye, cyanine dye, merocyanine dye, croconic acid (coronium) dye, squarylium dye, azulene dye, and dye mixtures containing the same
Figure BDA0003714954500000431
Pigment, polymethine pigment, naphthoquinone pigment, and pyrane
Figure BDA0003714954500000432
Dye, phthalocyanine dye, naphthalocyanine dye, naphthalimide dye, azo dye, condensed azo dye, indigo dye, pyreneketone dye, perylene dye, and perylene dye
Figure BDA0003714954500000433
Oxazine series of colorsPigments such as quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, thioindigo pigments, metal complex pigments (metal complex salt dyes), dithiol metal complex pigments, indoxyl pigments, triallyl methane pigments, anthraquinone pigments, naphthol pigments, azomethine pigments, benzimidazolone pigments, pyranthrone pigments and reducing pigments.
Examples of the inorganic pigment 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.
The colorant (J) contained in the second curable resin film (x2) and the second curable resin film-forming composition may be one kind or two or more kinds. When two or more kinds of the colorants (J) are used, the combination and ratio thereof can be arbitrarily selected.
When the colorant (J) is used, the content of the colorant (J) in the second curable resin film (x2) may be appropriately adjusted according to the purpose. For example, as described above, the second cured resin film (r2) which is a cured product formed by curing the second curable resin film (x2) may be printed by laser irradiation, and the print visibility may be adjusted by adjusting the content of the colorant (J) in the second curable resin (x2) or adjusting the light transmittance of the protective film. In addition, by adjusting the content of the colorant (J), the design of the protective film can be improved, and the grinding crack on the back surface of the semiconductor wafer can be made less likely to be observed. In view of these, in the second curable resin film-forming composition for forming the second curable resin film (x2), the ratio of the content of the colorant (J) to the total content of all components other than the solvent (also referred to as the total mass of the solid components of the second curable resin film-forming composition) (i.e., the content of the colorant (J) in the second curable resin film (x 2)) is preferably 0.1 to 10 mass%, more preferably 0.1 to 7.5 mass%, and particularly preferably 0.1 to 5 mass%. By setting the content of the colorant (J) to the lower limit or more, the effect of using the colorant (J) can be more remarkably obtained. When the content of the colorant (J) is not more than the upper limit, the transmittance of the second curable resin film (x2) can be prevented from decreasing.
The first curable resin film (x1) and the first curable resin film-forming composition may contain a colorant (J). However, from the viewpoint of ensuring the visibility of the lines to be divided of the wafer for manufacturing a semiconductor chip, the content of the colorant (J) is preferably an amount within a range that ensures transparency at a level that ensures the visibility of the lines to be divided.
The second support sheet (Y2) of the second composite sheet (α 2) may have the same configuration as the first support sheet (Y1). Specifically, the second support sheet (Y2) may be made of a material composed only of the base material 51 as shown in fig. 4, as in the first support sheet (Y1), may be a pressure-sensitive adhesive sheet composed of a laminate of the base material 51 and the pressure-sensitive adhesive layer 61 as shown in fig. 5, or may be a pressure-sensitive adhesive sheet composed of a laminate of the base material 51, the intermediate layer 71, and the pressure-sensitive adhesive layer 61 as shown in fig. 6.
The base material, the intermediate layer, and the adhesive layer of the second support sheet (Y2) may be the same in structure and material as the base material, the intermediate layer, and the adhesive layer of the first support sheet (Y1).
[ method of Using the first curable resin film (x1) ]
The first curable resin film (x1) is used for forming a cured resin film (first cured resin film (r1)) as a protective film on both the bump formation surface and the side surface of the semiconductor chip having the bump formation surface provided with bumps.
More specifically, the first curable resin film (x1) is used for forming a cured resin film (first cured resin film (r1)) as a protective film on both the bump formation surface and the side surface of the semiconductor chip having the bump formation surface provided with bumps, by a method for manufacturing a semiconductor chip, which will be described later, using a semiconductor chip manufacturing wafer having the bump formation surface provided with bumps and groove portions as lines to be divided.
[ method of Using the second curable resin film (x2) ]
The second curable resin film (x2) is used for forming a cured resin film (second cured resin film (r2)) as a protective film on the back surface of the semiconductor chip having the bump formation surface provided with bumps.
More specifically, the first curable resin film (x1) is used for forming a cured resin film (second cured resin film (r2)) as a protective film on the back surface of a semiconductor chip having a bump forming surface with bumps, by a process (T) of a semiconductor chip manufacturing method described later, which uses a semiconductor chip manufacturing wafer having a bump forming surface with bumps and groove portions as lines to be divided.
[ method of Using the first composite sheet (. alpha.1) ]
The first composite sheet (α 1) is used for forming a cured resin film (first cured resin film (r1)) as a protective film on both the bump formation surface and the side surface of a semiconductor chip having a bump formation surface provided with bumps.
More specifically, the first composite sheet (α 1) is used for forming a cured resin film (first cured resin film (r1)) as a protective film on both the bump formation surface and the side surface of a semiconductor chip having a bump formation surface provided with bumps by a method for manufacturing a semiconductor chip, which will be described later, using a wafer for manufacturing a semiconductor chip having a bump formation surface provided with bumps and grooves as planned dividing lines.
[ method of Using the second composite sheet (. alpha.2) ]
The second composite sheet (α 2) is used for forming a cured resin film (second cured resin film (r2)) as a protective film on the back surface of a semiconductor chip having a bump forming surface provided with bumps.
More specifically, the second composite sheet (α 2) is used for forming a cured resin film (second cured resin film (r2)) as a protective film on the back surface of a semiconductor chip having a bump-forming surface provided with bumps, in a step (T) of a method for manufacturing a semiconductor chip, which will be described later, using a wafer for manufacturing a semiconductor chip having a bump-forming surface provided with bumps and groove portions as lines to be divided.
[ method for manufacturing semiconductor chip of the present invention ]
Fig. 7 is a process diagram of a method for manufacturing a semiconductor chip according to the present invention.
The method for manufacturing a semiconductor chip of the present invention includes a step (S1) of preparing a wafer for manufacturing a semiconductor chip, a step (S2) of attaching a first composite sheet (α 1), a step (S3) of curing a first curable resin (x1), and a step (S4) of singulating the wafer, and further includes a step (S-BG) of grinding the back surface of the wafer for manufacturing a semiconductor chip.
In the method for manufacturing a semiconductor chip according to one embodiment of the present invention, the first curable resin film (x1) may be used, but the first composite sheet (α 1) is preferably used from the viewpoint of improving handling properties and the like.
Specifically, a method for manufacturing a semiconductor chip according to an embodiment of the present invention uses the first composite sheet (α 1) and includes the following steps (S1) to (S4) in this order.
Step (S1): preparing a wafer for manufacturing a semiconductor chip, in which grooves are formed as lines to be divided so as not to reach a back surface of a semiconductor wafer having a bump formation surface provided with bumps;
step (S2): pressing and adhering a first curable resin (x1) to the bump formation surface of the semiconductor chip production wafer, and filling the first curable resin (x1) into the groove formed in the semiconductor chip production wafer while covering the bump formation surface of the semiconductor chip production wafer with the first curable resin (x 1);
step (S3): curing the first curable resin (x1) to obtain a wafer for manufacturing a semiconductor chip having a first cured resin film (r 1);
step (S4): obtaining a semiconductor chip in which at least the bump formation surface and the side surface are covered with the first cured resin film (r1) by singulating the semiconductor chip-producing wafer with the first cured resin film (r1) along the planned dividing lines,
the method further includes the following step (S-BG) after the step (S2) and before the step (S3), after the step (S3) and before the step (S4), or in the step (S4).
Step (S-BG): grinding the back surface of the wafer for manufacturing semiconductor chips
By the manufacturing method including the above steps, a semiconductor chip can be obtained which is coated with the first cured resin film (r1) not only on the bump formation surface but also on the side surface, has excellent strength, and is less likely to cause peeling of the first cured resin film (r1) as a protective film.
Here, "coated" means that the first cured resin film (r1) is formed along the shape of at least the bump formation surface and the side surface of 1 semiconductor chip. That is, the present invention is clearly distinguished from a sealing technique in which a plurality of semiconductor chips are sealed in a resin.
Hereinafter, the method for manufacturing a semiconductor chip according to the present invention will be described in detail step by step.
In the following description, the "semiconductor chip" is simply referred to as a "chip", and the "semiconductor wafer" is simply referred to as a "wafer".
[ Process (S1) ]
Fig. 8 is a plan view and fig. 9 is a schematic sectional view of an example of the semiconductor wafer prepared in the step (S1).
In step (S1), a semiconductor chip manufacturing wafer 10 is prepared, in which grooves 13 are formed as lines to be divided in the bump forming surface 11a of the semiconductor wafer 11 having the bump forming surface 11a having the bumps 12 so as not to reach the back surface 11b of the semiconductor wafer 10.
In fig. 8, the bumps are not shown.
The shape of the bump 12 is not particularly limited, and may be any shape as long as it can be fixed in contact with an electrode or the like on a substrate for mounting a chip.
For example, in fig. 9, the bump 12 is formed in a spherical shape, but the bump 12 may be a spheroid. The spheroid may be, for example, a spheroid stretched in a direction perpendicular to the bump forming surface 11a of the wafer 11, or a spheroid stretched in a direction horizontal to the bump forming surface 11a of the wafer 11. Further, the bump 12 may be ピラー (pillar) shape.
The height of the bump 12 is not particularly limited, and may be appropriately changed according to design requirements.
For example, it is 30 to 300. mu.m, preferably 60 to 250. mu.m, and more preferably 80 to 200. mu.m.
Note that the "height of the bump 12" is a height of a portion located at the highest position from the bump forming surface 11a when 1 bump is focused.
The number of bumps 12 is not particularly limited, and may be appropriately changed according to design requirements.
The wafer 11 is a semiconductor wafer on the surface of which circuits such as wirings, capacitors, diodes, and transistors are formed. The material of the wafer is not particularly limited, and examples thereof include: silicon wafers, silicon carbide wafers, compound semiconductor wafers, glass wafers, sapphire wafers, and the like.
The size of the wafer 11 is not particularly limited, but is usually 8 inches (200 mm in diameter) or more, and preferably 12 inches (300 mm in diameter) or more, from the viewpoint of improving the batch processing efficiency. The shape of the wafer is not limited to a circular shape, and may be a square shape such as a square shape or a rectangular shape. In the case of a square wafer, the length of the longest side is preferably equal to or greater than the above dimension (diameter) in terms of the size of the wafer 11, from the viewpoint of improving the batch efficiency.
The thickness of the wafer 11 is not particularly limited, but is preferably 100 μm to 1,000 μm, more preferably 200 μm to 900 μm, and still more preferably 300 μm to 800 μm, from the viewpoint of easily suppressing warpage that occurs with shrinkage when the first curable resin (x1) is cured, and from the viewpoint of suppressing the amount of grinding of the back surface 11b of the wafer 11 in the subsequent step and shortening the time required for back surface grinding.
The bump formation surface 11a of the semiconductor chip manufacturing wafer 10 prepared in the step (S1) has a plurality of grooves 13 formed in a lattice shape as lines to be divided when the semiconductor chip manufacturing wafer 10 is singulated. The plurality of grooves 13 are grooves formed by a Dicing blade cutting method (Dicing blade cutting), and are formed to a depth shallower than the thickness of the wafer 11 so that the deepest portions of the grooves 13 do not reach the back surface 11b of the wafer 11. The plurality of grooves 13 can be formed by dicing using a conventionally known wafer dicing apparatus or the like provided with a dicing blade. The plurality of grooves 13 may be formed by cutting with a laser or the like without using a blade.
The plurality of grooves 13 need only be formed in a desired size and shape of the semiconductor chip to be manufactured, and the grooves 13 need not be formed in a lattice shape as shown in fig. 8. The size of the semiconductor chip is usually about 0.5mm × 0.5mm to 1.0mm × 1.0mm, but is not limited to this size.
From the viewpoint of improving the filling property of the first curable resin (x1), the width of the grooves 13 is preferably 10 to 2,000 μm, more preferably 30 to 1,000 μm, even more preferably 40 to 500 μm, and even more preferably 50 to 300 μm.
The depth of the groove 13 can be adjusted according to the thickness of the wafer used and the desired chip thickness, and is preferably 30 μ.
The aspect ratio of the groove 13 may be 2 to 6, 2.5 to 5, or 3 to 5.
The wafer 10 for manufacturing a semiconductor chip prepared in the step (S1) is subjected to a step (S2).
[ Process (S2) ]
Fig. 10 shows an outline of the process (S2).
In the step (S2), the first curable resin (x1) is pressed against and bonded to the bump formation surface 11a of the semiconductor chip manufacturing wafer 10.
Here, from the viewpoint of handling properties of the first curable resin (x1), the first curable resin (x1) is preferably used by being laminated on a support sheet.
Therefore, in the step (S2), it is preferable that the first composite sheet (α 1) having a laminated structure in which the first support sheet (Y1) and the layer (X1) of the first curable resin (X1) are laminated is pressed against the bump formation surface 11a of the semiconductor chip production wafer 10 with the layer (X1) as the bonding surface and bonded thereto.
Through the step (S2), as shown in fig. 10, the bump formation surface 11a of the semiconductor chip production wafer 10 is coated with the first curable resin (x1), and the first curable resin (x1) is filled in the groove portions 13 formed in the semiconductor chip production wafer 10.
By filling the grooves 13 formed in the semiconductor chip production wafer 10 with the first curable resin (x1), the portions to be the side surfaces of the semiconductor chips can be coated with the first curable resin (x1) when the semiconductor chip production wafer 10 is singulated in the step (S4). That is, a clad which is a precursor of the first cured resin film (r1) covering the side surface of the semiconductor chip and is necessary to suppress peeling of the first cured resin film (r1) as a protective film while making the strength of the semiconductor chip excellent can be formed by the process (S2).
The pressing force when the first composite sheet (α 1) is bonded to the semiconductor chip production wafer 10 is preferably 1kPa to 200kPa, more preferably 5kPa to 150kPa, and even more preferably 10kPa to 100kPa, from the viewpoint of improving the filling property of the first curable resin (x1) into the groove portions 13.
The pressing force for bonding the first composite sheet (α 1) to the semiconductor chip fabrication wafer 10 can be varied as appropriate from the initial stage to the final stage of the bonding. For example, from the viewpoint of improving the filling property of the first curable resin (x1) into the groove portion 13, it is preferable to set the pressing force at the initial stage of the adhesion to be low and gradually increase the pressing force.
When the first curable resin (x1) is a thermosetting resin when the first composite sheet (α 1) is bonded to the semiconductor chip fabrication wafer 10, heating is preferably performed from the viewpoint of improving the filling property of the first curable resin (x1) into the groove portions 13. When the first curable resin (x1) is a thermosetting resin, the fluidity of the first curable resin (x1) is temporarily improved by heating, and the first curable resin is cured by continuing heating. Therefore, by heating the first curable resin (x1) within a range in which the fluidity thereof is improved, the first curable resin (x1) can be easily distributed over the entire groove portion 13, and the filling property of the first curable resin (x1) into the groove portion 13 can be further improved.
The specific heating temperature (sticking temperature) is preferably 50 to 150 ℃, more preferably 60 to 130 ℃, and still more preferably 70 to 110 ℃.
The heat treatment performed on the first curable resin (x1) is not included in the curing treatment of the first curable resin (x 1).
Further, when the first composite sheet (α 1) is attached to the semiconductor chip production wafer 10, it is preferable to perform the attachment under a reduced pressure atmosphere. This allows the groove portions 13 to be under negative pressure, and the first curable resin (x1) to easily spread over the entire groove portions 13. As a result, the filling property of the first curable resin (x1) into the groove portion 13 becomes better. The specific pressure of the reduced-pressure atmosphere is preferably 0.001kPa to 50kPa, more preferably 0.01kPa to 5kPa, and still more preferably 0.05kPa to 1 kPa.
In addition, from the viewpoint of further improving the filling property of the first curable resin (X1) into the groove portions 13, the thickness of the layer (X1) of the first curable resin (X1) in the first composite sheet (α 1) is preferably greater than 30 μm and 200 μm or less, more preferably 60 to 150 μm, and still more preferably 80 to 130 μm.
Further, since the layer (X1) of the first curable resin (X1) is formed of the first curable resin (X1), the above-described condition (I) is satisfied. Therefore, since the X value is 19 or more and less than 10,000, when the first composite sheet (α 1) is attached to the bump formation surface 11a of the semiconductor chip production wafer 10, the effect of suppressing the first curable resin (X1) from remaining on the upper portion of the bump 12, the effect of suppressing the overflow of the layer (X1) of the first curable resin (X1), the effect of suppressing the shrinkage of the first cured resin film (r1) which is the first curable resin (X1) and a cured product thereof on the bump formation surface 11a are excellent, and the filling property of the first curable resin (X1) into the groove portions 13 is also excellent.
Here, the first support sheet (Y1) of the first composite sheet (α 1) preferably functions as a back grinding sheet while supporting the first curable resin (x 1).
In this case, when the back surface 11b of the wafer 11 is ground in a state where the first composite sheet (α 1) is bonded, the first support sheet (Y1) functions as a back grinding sheet, and the back grinding process can be easily performed.
[ Process (S3), Process (S4), and Process (S-BG) ]
By the steps up to the step (S2), a laminated body can be formed in which the first composite sheet (α 1) is laminated by being stuck to the wafer 10 for manufacturing a semiconductor chip. This laminate is preferably subjected to the steps according to any of the first to fourth embodiments described below, depending on the time point at which the step (S-BG) is performed.
Hereinafter, the first to fourth embodiments will be described with respect to the step (S3) and the step (S4) while inserting the description of the time point when the step (S-BG) is performed.
< first embodiment >
In the first embodiment, as shown in fig. 7, the step (S-BG) may be performed after the step (S2) and before the step (S3).
Fig. 11 shows a diagram relating to the first embodiment.
(first embodiment: Process (S-BG))
In the first embodiment, the step (S-BG) is first performed. Specifically, as shown in fig. 11 (1-a), the back surface 11b of the wafer 10 for manufacturing semiconductor chips is ground while the first composite sheet (α 1) is bonded thereto. "BG" in fig. 11 indicates back grinding, and the same applies to the following drawings. Next, as shown in fig. 11 (1-b), the first support sheet (Y1) was peeled off from the first composite sheet (α 1).
The amount of grinding when grinding the back surface 11b of the semiconductor chip production wafer 10 may be an amount that exposes at least the bottom portions of the groove portions 13 of the semiconductor chip production wafer 10, but the grinding may be further performed to grind the semiconductor chip production wafer 10 and also grind the first curable resin (x1) filled in the groove portions 13.
In the first embodiment, since the first support sheet (Y1) is peeled off before the step (S3) is performed, even when the first curable resin (x1) is a thermosetting resin and heat treatment for curing is performed in the step (S3), the first support sheet (Y1) is not required to have heat resistance. Therefore, the degree of freedom in design of the first support sheet (Y1) is improved.
(first embodiment: Process (S3))
After the step (S-BG) is performed, a step (S3) is performed. Specifically, as shown in fig. 11 (1-c), the first curable resin (x1) is cured to obtain a wafer 10 for manufacturing a semiconductor chip having a first cured resin film (r 1).
The first cured resin film (r1) formed by curing the first curable resin (x1) is stronger than the first curable resin (x1) at normal temperature. Therefore, by forming the first cured resin film (r1), the bump neck portion can be well protected. In the step (S4) shown in fig. 11 (1-d), the semiconductor chip manufacturing wafer 10 with the first cured resin film (r1) is singulated to obtain a semiconductor chip whose side surface is also covered with the first cured resin film (r1), whereby a semiconductor chip with excellent strength can be obtained. Further, peeling of the first cured resin film (r1) as a protective film can be suppressed.
(first embodiment: curing method)
The curing of the first curable resin (x1) may be performed by any of thermal curing and curing by energy ray irradiation, depending on the kind of curable component contained in the first curable resin (x 1).
The conditions for the thermal curing are preferably 100 to 200 ℃, more preferably 110 to 170 ℃, and particularly preferably 120 to 150 ℃. The heating time during the heat curing is preferably 0.5 to 5 hours, more preferably 0.5 to 4 hours, and particularly preferably 1 to 3 hours.
The conditions for curing by irradiation with energy rays may be appropriately set depending on the type of energy rays used, and for example, in the case of using ultraviolet rays, the illuminance is preferably 180 to 280mW/cm 2 The light amount is preferably 450 to 1000mJ/cm 2 。
Here, in the process of forming the first cured resin film (r1) by curing the first curable resin (x1), the first curable resin (x1) is preferably a thermosetting resin from the viewpoint of removing air bubbles and the like which may be mixed when the first curable resin (x1) is filled into the groove portions 13 in the step (S2). That is, when the first curable resin (x1) is a thermosetting resin, the fluidity of the first curable resin (x1) is temporarily improved by heating, and the first curable resin is cured by continuing heating. By utilizing this phenomenon, it is possible not only to remove air bubbles or the like that may be mixed when filling the groove portions 13 with the first curable resin (x1) when the fluidity of the first curable resin (x1) is improved, thereby achieving a more favorable state of filling the groove portions 13 with the first curable resin (x1), but also to cure the first curable resin (x 1).
In addition, the first curable resin (x1) is preferably an energy ray curable resin from the viewpoint of shortening the curing time.
The first curable resin (x1) for forming the first cured resin film (r1) is described in detail below.
(first embodiment: Process (S4))
After the step (S3), a step (S4) is performed. Specifically, as shown in fig. 11 (1-d), the first cured resin film (r1) of the semiconductor chip-producing wafer 10 with the first cured resin film (r1) is cut along the dividing lines at the portions where the grooves are to be formed.
Cutting can be performed by a conventionally known method such as a blade cutting method or a laser cutting method.
Thus, the semiconductor chip 40 in which at least the bump formation surface 11a and the side surfaces are covered with the first cured resin film (r1) can be obtained.
The semiconductor chip 40 has excellent strength because the bump forming surface 11a and the side surfaces are covered with the first cured resin film (r 1). Since the bump formation surface 11a and the side surfaces are continuously covered with the first cured resin film (r1) without interruption, the bonding surface (interface) between the bump formation surface 11a and the first cured resin film (r1) is not exposed at the side surfaces of the semiconductor chip 40. An exposed portion exposed on a side surface of the semiconductor chip 40 in a bonding surface (interface) between the bump formation surface 11a and the first cured resin film (r1) is likely to be a starting point of film peeling. Since the semiconductor chip 40 of the present invention does not have the exposed portion, film peeling from the exposed portion is less likely to occur during and after the manufacturing of the semiconductor chip 40 by cutting the semiconductor chip manufacturing wafer 10. Therefore, the semiconductor chip 40 in which peeling of the first cured resin film (r1) as the protective film is suppressed can be obtained.
In the step (S4), when the portion of the first cured resin film (r1) of the semiconductor chip-manufacturing wafer 10 with the first cured resin film (r1) formed in the groove portion is cut along the planned dividing line, the first cured resin film (r1) is preferably transparent. Since the semiconductor wafer 11 is seen through the first cured resin film (r1) being transparent, visibility of the lines to be divided can be ensured. This facilitates cutting along the lines to be divided.
< second embodiment >
In the second embodiment, as shown in fig. 7, the process (S-BG) may be performed after the process (S3) and before the process (S4).
Fig. 12 shows a schematic diagram relating to the second embodiment.
(second embodiment: Process (S3))
In the second embodiment, first, the step (S3) is performed. Specifically, as shown in fig. 12 (2-a), the first curable resin (x1) is cured in a state where the first composite sheet (α 1) is bonded, thereby obtaining the semiconductor chip-producing wafer 10 with the first cured resin film (r 1).
The first cured resin film (r1) formed by curing the first curable resin (x1) is stronger than the first curable resin (x1) at normal temperature. Therefore, by forming the first cured resin film (r1), the bump neck portion can be well protected. In the step (S4), the semiconductor chip manufacturing wafer 10 with the first cured resin film (r1) is singulated to obtain semiconductor chips whose side surfaces are also covered with the first cured resin film (r1), whereby semiconductor chips with excellent strength can be obtained. Further, peeling of the first cured resin film (r1) as a protective film can be suppressed.
The curing method may be the same as the curing method described in the first embodiment.
By performing the thermosetting treatment without peeling the first support sheet (Y1), the first support sheet (Y1) can suppress the flow on the surface of the first curable resin (x1) which temporarily occurs when curing the first curable resin (x1) at the time of thermosetting, and the flatness of the first cured resin film (r1) on the bump formation surface can be improved. Further, by curing the first curable resin (x1) before grinding the back surface 11b of the semiconductor chip fabrication wafer 10, warpage of the semiconductor chip fabrication wafer 10 can be suppressed.
(second embodiment: Process (S-BG))
After the step (S3), a step (S-BG) is performed. As shown in fig. 12 (2-b), the back surface 11b of the semiconductor chip production wafer 10 is ground in a state where the first composite sheet (α 1) is bonded thereto.
The amount of grinding when grinding the back surface 11b of the semiconductor chip production wafer 10 may be an amount that exposes at least the bottom portions of the groove portions 13 of the semiconductor chip production wafer 10, but the grinding may be further performed to grind the semiconductor chip production wafer 10 and also grind the first cured resin film (r1) filled in the groove portions 13.
Next, as shown in fig. 12 (2-c), the first support sheet (Y1) was peeled off from the first composite sheet (α 1).
(second embodiment: Process (S4))
After the step (S-BG) is performed, the step (S4) is performed in the same manner as in the first embodiment. Specifically, as shown in fig. 12 (2-d), the first cured resin film (r1) of the semiconductor chip-producing wafer 10 with the first cured resin film (r1) is cut along the dividing lines at the portions where the grooves are to be formed.
Cutting can be performed by a conventionally known method such as a blade cutting method or a laser cutting method.
Thus, the semiconductor chip 40 in which at least the bump formation surface 11a and the side surfaces are covered with the first cured resin film (r1) can be obtained.
The semiconductor chip 40 has excellent strength because the bump formation surface 11a and the side surfaces are covered with the first cured resin film (r 1). In addition, for the reasons described above, the semiconductor chip 40 in which peeling of the first cured resin film (r1) as the protective film is suppressed can be obtained.
< third embodiment >
In the third embodiment, the second embodiment is common in that the process (S-BG) may be performed after the process (S3) and before the process (S4) as shown in fig. 7. But differs from the second embodiment in that a back grinding sheet (b-BG) is additionally used.
Fig. 13 shows a diagram relating to a third embodiment.
(third embodiment: Process (S3))
In the third embodiment, the step (S3) is first performed, but before that, as shown in fig. 13 (3-a), the first support sheet (Y1) is peeled from the first composite sheet (α 1). Then, the process is performed (S3). Specifically, as shown in fig. 13 (3-b), the first curable resin (x1) is cured to obtain the wafer 10 for manufacturing a semiconductor chip with the first cured resin film (r 1).
The curing method may be the same as the curing method described in the first embodiment.
Since the first support sheet (Y1) is peeled off before the step (S3) is performed, even when the first curable resin (x1) is a thermosetting resin and heat treatment for curing is performed in the step (S3), heat resistance is not required for the first support sheet (Y1). Therefore, the degree of freedom in design of the first support sheet (Y1) is improved.
Further, by curing the first curable resin (x1) before grinding the back surface 11b of the semiconductor chip fabrication wafer 10, warpage of the semiconductor chip fabrication wafer 10 can be suppressed.
(third embodiment: Process (S-BG))
After the step (S3), a step (S-BG) is performed. Specifically, as shown in (3-c) of fig. 13, the back grinding sheet (b-BG) is stuck to the surface of the first cured resin film (r1) of the wafer 10 for manufacturing a semiconductor chip having the first cured resin film (r 1). Next, as shown in fig. 13 (3-d), after the back surface 11b of the semiconductor chip fabrication wafer 10 is ground in a state where the back grinding flake (b-BG) is attached, as shown in fig. 13 (3-e), the back grinding flake (b-BG) is peeled off from the semiconductor chip fabrication wafer 10 with the first cured resin film (r 1).
Since the back grinding sheet (b-BG) is not used in the step (S3), even when the first curable resin (x1) is a thermosetting resin and the heating process for curing is performed in the step (S3), the back grinding sheet (b-BG) is not required to have heat resistance. Therefore, the degree of freedom in design of the back grinding sheet (b-BG) is improved.
The amount of grinding when grinding the back surface 11b of the semiconductor chip preparation wafer 10 may be an amount that exposes at least the bottom of the groove 13 of the semiconductor chip preparation wafer 10, but the grinding may be performed further so that the first cured resin film (r1) filled in the groove 13 is ground at the same time as the grinding of the semiconductor chip preparation wafer 10.
(third embodiment: Process (S4))
After the step (S-BG) is performed, the step (S4) is performed in the same manner as the first and second embodiments. Specifically, as shown in fig. 13 (3-f), the first cured resin film (r1) of the semiconductor chip-producing wafer 10 with the first cured resin film (r1) is cut along the dividing lines at the portions where the grooves are to be formed.
The cutting can be performed by a conventionally known method such as a blade cutting method or a laser cutting method.
Thus, the semiconductor chip 40 in which at least the bump formation surface 11a and the side surfaces are covered with the first cured resin film (r1) can be obtained.
The semiconductor chip 40 has excellent strength because the bump forming surface 11a and the side surfaces are covered with the first cured resin film (r 1). Further, for the reasons described above, the semiconductor chip 40 in which peeling of the first cured resin film (r1) as the protective film is suppressed can be obtained.
< fourth embodiment >
In the fourth embodiment, as shown in fig. 7, the step (S-BG) may be performed in the step (S4).
Fig. 14 shows a diagram relating to the fourth embodiment.
(fourth embodiment: Process (S3))
In the fourth embodiment, the step (S3) is first performed, but before that, as shown in fig. 14 (4-a), the first support sheet (Y1) is peeled off from the first composite sheet (α 1). Then, the process is performed (S3). Specifically, as shown in fig. 14 (4-b), the first curable resin (x1) is cured to obtain a wafer 10 for manufacturing a semiconductor chip having a first cured resin film (r 1).
The curing method may be the same as the curing method described in the first embodiment.
Since the first support sheet (Y1) is peeled off before the step (S3) is performed, even when the first curable resin (x1) is a thermosetting resin and heat treatment for curing is performed in the step (S3), heat resistance is not required for the first support sheet (Y1). Therefore, the degree of freedom in design of the first support sheet (Y1) is improved.
In addition, by curing the first curable resin (x1) before grinding the back surface 11b of the semiconductor chip fabrication wafer 10, warpage of the semiconductor chip fabrication wafer 10 can be suppressed.
(fourth embodiment: Process (S4) including Process (S-BG))
After the step (S3) is performed, as shown in fig. 14 (4-c), in the first cured resin film (r1) of the semiconductor chip-manufacturing wafer 10 with the first cured resin film (r1), the portions formed in the groove portions 13 are cut into cuts along the planned dividing lines. From the viewpoint of ease of singulation, the depth of the cut is preferably set to a depth reaching the deepest portion of the groove portion 13. Thus, in the step (S-BG) described later, the semiconductor chip production wafer 10 with the first cured resin film (r1) can be singulated along the cut.
Alternatively, although not shown, the modified regions may be formed along the planned dividing lines at the portions of the first cured resin film (r1) of the semiconductor chip-manufacturing wafer 10 with the first cured resin film (r1) that are formed in the groove portions 13. The modified region may be formed by laser or plasma treatment or the like. As a result, in the step (S-BG) described later, cracks are generated from the modified region as a starting point, and the semiconductor chip manufacturing wafer 10 with the first cured resin film (r1) is singulated along the modified region.
Next, the step (S-BG) is performed. Specifically, as shown in fig. 14 (4-d), a back grinding sheet (b-BG) is attached to the surface of the first cured resin film (r1) of the semiconductor chip production wafer 10 having the first cured resin film (r 1). Next, as shown in fig. 14 (4-e), the back surface 11b of the semiconductor chip production wafer 10 is ground with the back grinding pad (b-BG) attached. Finally, as shown in (4-f) of fig. 14, the back grinding sheet (b-BG) was peeled off from the semiconductor chip production wafer 10 with the first cured resin film (r 1).
Thus, the semiconductor chip 40 in which at least the bump formation surface 11a and the side surfaces are covered with the first cured resin film (r1) can be obtained.
The amount of grinding when grinding the back surface 11b of the semiconductor chip production wafer 10 may be an amount that exposes at least the bottom portions of the groove portions 13 of the semiconductor chip production wafer 10, but the grinding may be further performed to grind the semiconductor chip production wafer 10 and also grind the first cured resin film (r1) filled in the groove portions 13.
The semiconductor chip 40 has excellent strength because the bump forming surface 11a and the side surfaces are covered with the first cured resin film (r 1).
Since the back grinding sheet (b-BG) is not used in the step (S3), even when the first curable resin (x1) is a thermosetting resin and the heating process for curing is performed in the step (S3), the back grinding sheet (b-BG) is not required to have heat resistance. Therefore, the degree of freedom in design of the back grinding piece (b-BG) is improved.
Here, in the first to fourth embodiments, the description has been given by exemplifying the mode in which the first support sheet (Y1) or the back-grinding sheet (b-BG) is used in the step (S-BG), but in one embodiment of the present invention, the resin layer (Z1) for back-grinding may be formed instead of the first support sheet (Y1) or the back-grinding sheet (b-BG).
Specifically, the grinding step may be performed instead of using the back grinding plate by coating the surface of the first cured resin film (r1) with a flowable resin (Z1) and coating the bumps exposed from the first cured resin film (r1) and then curing the resin (Z1) to form the resin layer (Z1) for back grinding.
When the surface of the first cured resin film (r1) and the bumps exposed from the first cured resin film (r1) are coated with the resin (Z1), the resin layer (Z1) for back grinding, which is no longer necessary, can be easily peeled off after the step (S-BG) by coating the surface of the first cured resin film (r1) and the bumps exposed from the first cured resin film (r1) with the resin (Z2) having flexibility so as to follow the unevenness of the bumps.
[ Process (T) ]
In one embodiment of the method for manufacturing a semiconductor chip according to the present invention, the method preferably further includes the following step (T).
Step (T): a step of forming a second cured resin film (r2) on the back surface of the wafer for manufacturing semiconductor chips
According to the manufacturing method of the above embodiment, the semiconductor chip 40 in which at least the bump formation surface 11a and the side surfaces are covered with the first cured resin film (r1) can be obtained. However, the back surface of the semiconductor chip 40 is exposed. Therefore, the step (T) is preferably performed from the viewpoint of protecting the back surface of the semiconductor chip 40 and further improving the strength of the semiconductor chip 40.
More specifically, the step (T) preferably includes the following steps (T1) to (T2) in this order.
Step (T1): a step of adhering a second curable resin (x2) to the back surface of the wafer for manufacturing the semiconductor chip
Step (T2): a step of curing the second curable resin (x2) to form a second curable resin film (r2)
In the step (T1), it is preferable to use a second composite sheet (α 2) having a laminated structure in which a second support sheet (Y2) and a layer (X2) of a second curable resin (X2) are laminated. Specifically, the step (T1) is preferably a step of attaching a second composite sheet (α 2) having a laminated structure in which a layer (X2) of a second support sheet (Y2) and a second curable resin (X2) is laminated to the back surface of the wafer for manufacturing semiconductor chips, with the layer (X2) as an attachment surface.
In this case, the time point when the second support sheet (Y2) is peeled off from the second composite sheet (α 2) may be between the step (T1) and the step (T2) or may be after the step (T2).
Here, when the second composite sheet (α 2) is used in the step (T1), the second support sheet (Y2) of the second composite sheet (α 2) preferably has a function as a dicing sheet while supporting the second curable resin (x 2).
In the case of the manufacturing methods according to the first to third embodiments, the second composite sheet (α 2) is bonded to the back surface 11b of the semiconductor chip production wafer 10 with the first cured resin film (r1) in the step (S4), whereby the second support sheet (Y2) functions as a dicing sheet when singulation is performed by dicing, and dicing can be easily performed.
Here, when the step (S3) is performed after the step (S-BG), as in the manufacturing method of the first embodiment, the step (T1) may be performed before the step (S3), and then the step (S3) and the step (T2) may be performed at the same time. That is, the first curable resin (x1) and the second curable resin (x2) may be simultaneously cured at once. This can reduce the number of curing processes.
Specifically, in the production method of the first to third embodiments, the step (T) includes the following step (T1-1) and the following step (T1-2) in this order,
step (T1-1): a step of attaching a second curable resin (x2) to the back surface of the wafer for manufacturing semiconductor chips after the step (S-BG) and before the step (S4)
Step (T1-2): a step of curing the second curable resin (x2) to form a second cured resin film (r2) before or after the step (S4)
In the step (S4), when the portion of the first cured resin film (r1) of the wafer for manufacturing semiconductor chips having the first cured resin film (r1) formed in the groove portions is cut along the lines to be divided, it is preferable to cut the second curable resin (x2) or the second cured resin film (r2) at once.
In the production method of the fourth embodiment, the step (T) includes the following step (T2-1) and the following step (T2-2) in this order,
step (T2-1): after the step (S-BG) and after the step (S4), a step of adhering a second curable resin (x2) to the back surface of the wafer for manufacturing a semiconductor chip while maintaining the back grinding sheet (b-BG) adhered thereon
Step (T2-2): a step of curing the second curable resin (x2) to form a second cured resin film (r2)
Preferably, the step (T) further comprises the following step (T2-3) before or after the step (T2-2).
Step (T2-3): a step of dividing the second curable resin layer (x2) or the second curable resin film (r2) along a curve
[ other Processes ]
In one embodiment of the method for manufacturing a semiconductor chip of the present invention, other steps may be included within a range not departing from the gist of the present invention.
Examples of such a process include a wet etching process and a dry etching process performed on the bump formation surface after the formation of the protective film (first cured resin film (r 1)).
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples.
1. Raw Material for producing first thermosetting resin film-Forming composition (x1-1-1)
The raw materials used for producing the first thermosetting resin film-forming composition (x1-1-1) are as follows.
(1) Polymer component (A)
(A) -1: polyvinyl butyral having a structural unit represented by the following formulae (i) -1, (i) -2 and (i) -3) (S-LEC BL-10, manufactured by Water-gas chemical industries, Ltd., weight average molecular weight 25000, glass transition temperature 59 ℃ C.).
(A) -2: an acrylic resin (weight average molecular weight 800,000, glass transition temperature-28 ℃) obtained by copolymerizing butyl acrylate (55 parts by mass), methyl acrylate (10 parts by mass), glycidyl methacrylate (20 parts by mass), and 2-hydroxyethyl acrylate (15 parts by mass).
[ chemical formula 2]
Figure BDA0003714954500000591
(in the formula, /) 1 About 28, m 1 Is 1 to 3, n 1 Is an integer of 68 to 74. )
(2) Epoxy resin (B1)
(B1) -1: liquid modified bisphenol A type epoxy resin ("EPICLON EXA-4850-150", available from DIC corporation, molecular weight 900, epoxy equivalent 450g/eq)
(B1) -2: liquid bisphenol F type epoxy resin (YL 983U, product of Mitsubishi chemical corporation, epoxy equivalent 165-175 g/eq)
(B1) -3: polyfunctional aromatic epoxy resin ("EPPN-502H" manufactured by Nippon Kabushiki Kaisha), epoxy equivalent of 158 to 178g/eq)
(B1) -4: dicyclopentadiene type epoxy resin (EPICLON HP-7200HH available from DIC corporation, epoxy equivalent 254-264 g/eq)
(3) Thermosetting agent (B2)
(B2) -1: novolac type phenol resin (BRG-556, a product of Showa Denko K.K.)
(B2) -2: o-cresol novolak resin (Phenolite KA-1160 "available from DIC corporation)
(4) Curing accelerator (C)
(C) -1: 2-phenyl-4, 5-dihydroxymethylimidazole ("Curezol 2 PHZ-PW" manufactured by Siguo chemical industries Co., Ltd.)
(5) Filler (D)
(D) -1: spherical silica modified with epoxy group (Adamano YA050C-MKK, manufactured by Admatechs, Ltd., average particle diameter 50nm)
(6) Additive (I)
(I) -1: surfactant (acrylic acid Polymer, "BYK-361N" manufactured by BYK Co., Ltd.)
(I) -2: silicone oil (aralkyl modified silicone oil, Momentive Performance Materials Japan K.K. "XF 42-334")
(I) -3: rheology modifier (polyhydroxycarboxylate, "BYK-R606" available from BYK Co., Ltd.)
2. Examples 1 to 2 and comparative examples 1 to 3
2-1 example 1
(1) Production of first thermosetting resin film-Forming composition (x1-1-1)
A composition (x1-1-1) for forming a thermosetting resin film, in which the total concentration of all components except a solvent was 45 mass%, was obtained by dissolving or dispersing polymer component (A) -1(100 parts by mass), epoxy resin (B1) -1(350 parts by mass), epoxy resin (B1) -4(270 parts by mass), thermosetting agent (B2) -1(190 parts by mass), curing accelerator (C) -1(2 parts by mass), filler (D) -1(90 parts by mass), and additive (I) -3(9 parts by mass) in methyl ethyl ketone and stirring at 23 ℃. The amounts of components other than the solvent to be blended shown here are all amounts of the target product not including the solvent.
(2) Production of first thermosetting resin film (x1-1)
A first thermosetting resin film (x1-1) having a thickness of 45 μm was formed by applying the composition (x1-1-1) obtained above to a release-treated surface of a release film (SP-PET 381031 manufactured by Lindchoku K.K., having a thickness of 38 μm) obtained by subjecting one surface of a polyethylene terephthalate film to a release treatment by a silicone treatment, and drying the composition by heating at 120 ℃ for 2 minutes.
2-2 example 2 and comparative examples 1 to 3
A first thermosetting resin film (x1-1) having a thickness of 45 μm was formed in the same manner as in example 1, except that either or both of the kind and the amount of the components to be blended in the production of the first thermosetting resin film-forming composition (x1-1-1) were changed so that the kind and the amount of the components contained in the first thermosetting resin film-forming composition (x1-1-1) were as shown in table 1 below.
In addition, when the column containing the component in table 1 is indicated as "-", it indicates that the first thermosetting resin film-forming composition (x1-1-1) does not contain the component.
3. Evaluation of
3-1. manufacture of the first composite sheet (. alpha.1)
A back-grinding tape ("E-8510 HR", manufactured by Lindecoke corporation) was used as the first support sheet (Y1), and was bonded to each of the first thermosetting resin films (x1-1) on the release films of examples 1 to 2 and comparative examples 1 to 3 obtained as described above. Thus, a first composite sheet (α 1) was obtained in which the first support sheet (Y1) and the first thermosetting resin film (x1-1) were laminated.
3-2 measurement of Gc1 and Gc300 of the first thermosetting resin film (X1-1), calculation of X value
20 pieces of a first thermosetting resin film (x1-1) having a thickness of 50 μm were produced in the same manner as described above, except that the amount of the composition (x1-1-1) applied was changed. Subsequently, these first thermosetting resin films (x1-1) were laminated, and the resulting laminated film was cut into a disk shape having a diameter of 25mm, thereby producing a test piece of the first thermosetting resin film (x1-1) having a thickness of 1 mm.
The place where the test piece was set in the viscoelasticity measuring apparatus ("MCR 301" manufactured by Anton Paar) was previously kept at 90 ℃, the test piece of the first thermosetting resin film (x1-1) obtained above was placed on the place, and the measuring tool was pressed against the upper surface of the test piece, thereby fixing the test piece to the place.
Then, the strain generated in the test piece was increased in stages in a range of 0.01% to 1000% under the conditions of a temperature of 90 ℃ and a measurement frequency of 1Hz, and the storage modulus Gc of the test piece was measured. Then, the X value is calculated from the measurement values of Gc1 and Gc 300. The results are shown in Table 1.
3-3 measurement of the amount of bleeding of the first thermosetting resin film (x1-1)
A first thermosetting resin film (x1-1) having a thickness of 30 μm was formed by applying the composition (x1-1-1) obtained above to a release-treated surface of a release film (SP-PET 381031 manufactured by Lindchoku K.K., having a thickness of 38 μm) obtained by subjecting one surface of a polyethylene terephthalate film to a release treatment by a silicone treatment, and drying the composition by heating at 120 ℃ for 2 minutes.
Subsequently, the first thermosetting resin film (x1-1) was processed into a circular shape having a diameter of 170mm together with the release film, thereby producing a test piece with a release film.
The entire exposed surface of the obtained test piece (in other words, the surface opposite to the side having the release film) was bonded to the surface of a transparent tape-like back-grinding tape ("E-8180" manufactured by leidenko corporation), thereby obtaining a laminate shown in fig. 15. Fig. 15 is a plan view schematically showing a state where the resulting laminate is viewed from above and downward of the back-grinding tape side thereof.
As shown in the figure, the obtained laminate 101 was composed of the back grinding tape 7, the test piece (first thermosetting resin film (x1-1)), and the release film laminated in this order in the thickness direction thereof.
Next, the release film was removed from the obtained laminate, and the newly generated exposed surface of the test piece (in other words, the surface of the test piece opposite to the side provided with the back-grinding tape) was pressed against one surface of a silicon wafer having a diameter of 12 inches, thereby bonding the test piece to the surface of the silicon wafer. In this case, the test piece was bonded by heating the first thermosetting resin film (x1-1) under conditions of a table temperature of 90 ℃, a bonding speed of 2mm/sec, a bonding pressure of 0.5MPa, and a roll bonding height of-200 μm using a bonding apparatus ("RAD-3510F/12" manufactured by Lindcgke Co., Ltd.).
Next, the maximum value of the length of the line segment connecting two different points on the outer periphery of the test piece with the back grinding tape attached to the silicon wafer was measured, and the amount of overflow (mm) of the test piece (in other words, the first thermosetting resin film (x1-1)) was calculated by the method described with reference to fig. 2 using the measured value (the maximum value of the length of the line segment). The results are shown in Table 1.
When the amount of the overflow was 170mm, it was judged that there was no change in shape with respect to the original test piece and no overflow occurred. On the other hand, when the amount of overflow exceeded 170mm, it was judged that there was a change in shape with respect to the original test piece and overflow occurred.
3-4 confirmation of Presence or absence of first thermosetting resin film (x1-1) remaining on the upper portion of bump
The release film was removed from the first composite sheet (α 1) obtained in "3-1. production of first composite sheet (α 1)", and the surface (exposed surface) of the first thermosetting resin film (x1-1) thus exposed was pressed against the bump forming surface of the semiconductor wafer having a bump of 8-inch diameter, whereby the first composite sheet (α 1) from which the release film was removed was adhered to the bump forming surface of the semiconductor wafer. In this case, a semiconductor wafer having a bump height of 210 μm, a bump width of 250 μm, and a distance between bumps of 400 μm was used. The first composite sheet (. alpha.1) was bonded while heating the first composite sheet (. alpha.1) using a bonding apparatus ("RAD-3510F/12" manufactured by Lindceko corporation) under conditions of a table temperature of 90 ℃, a bonding speed of 2mm/sec, a bonding pressure of 0.5MPa, and a roll bonding height of-200 μm.
Subsequently, the first support sheet (Y1) was removed from the first thermosetting resin film (x1-1) by using a multichip chip mounter ("RAD-2700F/12" manufactured by Lindcao K.K.) to expose the first thermosetting resin film (x 1-1).
Next, the presence or absence of the residue of the first thermosetting resin film (x1-1) on the upper portion of the bump was confirmed by observing the surface of the bump of the semiconductor wafer from a direction forming an angle of 60 ° with respect to the direction perpendicular to the bump formation surface of the semiconductor wafer using a scanning electron microscope (SEM, VE-9700, manufactured by KEYENCE). Here, the determination is "with residue" when residue is present on the bump, and the determination is "without residue" when residue is not present on the bump. The results are shown in Table 1.
3-5 confirmation of Presence or absence of shrinkage of first thermosetting resin film (x1-1) on bump formation surface
A12-inch semiconductor wafer on which no bump was formed was used for the presence or absence of a shrinkage cavity caused by the cured product of the first thermosetting resin film (x1-1) on the surface of the semiconductor chip on the bump formation surface.
Specifically, the first composite sheet (α 1) was bonded to a 12-inch silicon wafer without bumps by the same method as in the case of "3-4" confirmation of presence or absence of the first thermosetting resin film (x1-1) remaining on the upper portions of the bumps ", and the first support sheet (Y1) was removed from the first thermosetting resin film (x 1-1).
Subsequently, the first thermosetting resin film (x1-1) adhered to the semiconductor wafer was heat-cured by heating the first thermosetting resin film in a pressurized oven ("RAD-9100" manufactured by Linekec corporation) at 130 ℃ for 2 hours under a furnace pressure of 0.5 MPa.
Subsequently, the entire laminate of the cured product of the first thermosetting resin film (x1-1) (the 1 st cured resin film (r1)) and the semiconductor wafer was observed from the cured product side using an optical microscope (VHX-1000, manufactured by KEYENCE corporation). Among them, the case where there is a region where the exposure of the semiconductor wafer can be directly confirmed is determined as "having a shrinkage cavity", and the case where there is no region where the exposure of the semiconductor wafer can be directly confirmed is determined as "having no shrinkage cavity".
3-5 evaluation of filling Property into groove portion
(1) Preparation of wafer for semiconductor chip fabrication
As a wafer for manufacturing a semiconductor chip, a 12-inch silicon wafer (wafer thickness 750 μm) obtained by half-cutting a line to be divided was used. The silicon wafer had a half-cut portion with a width of 60 μm (width of the groove portion) and a groove depth of 230 μm.
(2) Evaluation method
The release film was removed from the first composite sheet (α 1) obtained in "3-1. production of first composite sheet (α 1)", and the surface side (half-cut formed surface) of the semiconductor chip fabrication wafer was bonded to the side of the edge under the conditions below the surface (exposed surface) of the first thermosetting resin film (x1-1) exposed thereby.
The pasting device: full-automatic laminating machine (product name "RAD-3510" manufactured by Lindeke corporation)
Roll pressure: 0.5MPa
Roller height: 400 μm
Pasting speed: 5mm/sec
Pasting temperature: 90 deg.C
Subsequently, the first support sheet (Y1) was peeled from the first thermosetting resin film (x1-1), and then the semiconductor chip-manufacturing wafer to which the first thermosetting resin film (x1-1) was attached was heated at 130 ℃ for 4 hours to be cured, thereby forming a first cured resin film (r 1). Then, the semiconductor chip production wafer was cut from the half-cut formation surface to the back surface, and the filling of the first cured resin film (r1) into the groove portion of the half-cut portion was observed with an optical microscope (VHX-1000, manufactured by KEYENCE).
The evaluation criteria for filling-in property are as follows.
S: no deformation in shape of the first cured resin film (r1) was observed, and the filling property was the best.
A: the shape of the first cured resin film (r1) was deformed in the vicinity of the entrance of the groove, but the filling property was good.
B: the filling property was poor.
4. Results
The components contained in the first thermosetting resin film-forming composition (x1-1-1) and the evaluation results are shown in table 1.
FIG. 16 shows the results of "evaluation of filling property into grooves" (photograph instead of drawing).
[ Table 1]
Figure BDA0003714954500000651
The following are known from the results shown in table 1.
It is understood that in examples 1 and 2 in which the value X is 19 or more and less than 10,000, no overflow was observed, no residue on the bump was left, no sink was observed at the time of pasting, and the filling property of the groove was good.
In contrast, when the X value is less than 19 as in comparative examples 1 and 3, it is understood that any one or more of the following occurs: overflow occurs, residue is generated on the upper part of the bump, and the filling property is poor.
It is also understood from the drawings of fig. 16 that the groove filling property is deteriorated when the overflow occurs as in comparative example 1, instead of the photograph. In addition, in comparative example 3, the first thermosetting resin film (x1-1) did not enter the groove.
Further, it is found that when the value of X is 10,000 or more as in comparative example 2, a crater is generated on the bump formation surface.
From the above results, it was found that a semiconductor chip having a bump formation surface and side surfaces well covered with the first cured resin film (r1) can be obtained by subjecting a wafer for manufacturing a semiconductor chip with the first cured resin film (r1) formed using the first thermosetting resin film (x1-1) of examples 1 and 2 to the above step (S4) and step (S-BG) and dividing the wafer into individual pieces.

Claims (14)

1. A curable resin film for forming a cured resin film as a protective film on both a bump formation surface and a side surface of a semiconductor chip having the bump formation surface, the bump formation surface being provided with bumps, the curable resin film satisfying the following condition (I),
< Condition (I) >
A test piece of the curable resin film having a diameter of 25mm and a thickness of 1mm is strained at a temperature of 90 ℃ and a frequency of 1Hz, and the storage modulus of the test piece is measured, wherein when the storage modulus of the test piece when the strain of the test piece is 1% is Gc1 and the storage modulus of the test piece when the strain of the test piece is 300% is Gc300, the value of X calculated by the following formula (i) is 19 or more and less than 10,000,
X＝Gc1/Gc300····(i)。
2. the curable resin film according to claim 1,
in the condition (I), Gc300 is less than 15,000.
3. A composite sheet for forming a cured resin film as a protective film on both a bump formation surface and a side surface of a semiconductor chip having the bump formation surface provided with bumps,
the composite sheet has a laminated structure in which a support sheet and a layer of a curable resin are laminated,
the curable resin is the curable resin film according to claim 1 or 2.
4. A method of use, the method comprising:
the curable resin film according to claim 1 or 2 is used for forming a cured resin film as a protective film on both the bump formation surface and the side surface of a semiconductor chip having a bump formation surface provided with bumps.
5. A method of use, the method comprising:
the composite sheet according to claim 3 is used for forming a cured resin film as a protective film on both the bump formation surface and the side surface of a semiconductor chip having a bump formation surface provided with bumps.
6. A method for manufacturing a semiconductor chip, comprising the following steps (S1) to (S4) in this order,
step (S1): preparing a wafer for manufacturing a semiconductor chip, in which grooves are formed as lines to be divided so as not to reach a back surface of a semiconductor wafer having a bump formation surface provided with bumps;
step (S2): pressing and adhering a first curable resin (x1) to the bump formation surface of the semiconductor chip production wafer, and filling the first curable resin (x1) into the groove portion formed in the semiconductor chip production wafer while covering the bump formation surface of the semiconductor chip production wafer with the first curable resin (x 1);
step (S3): a step of curing the first curable resin (x1) to obtain a wafer for manufacturing a semiconductor chip having a first cured resin film (r 1);
step (S4): obtaining a semiconductor chip in which at least the bump formation surface and the side surface are covered with the first cured resin film (r1) by singulating the semiconductor chip-manufacturing wafer with the first cured resin film (r1) along the planned dividing lines,
further comprising a step (S-BG) after the step (S2) and before the step (S3), after the step (S3) and before the step (S4), or in the step (S4),
step (S-BG): a step of grinding the back surface of the wafer for manufacturing semiconductor chips,
the curable resin film according to claim 1 or 2 is used as the first curable resin (x 1).
7. The method for manufacturing a semiconductor chip according to claim 6,
the step (S2) is performed by: a first composite sheet (alpha 1) having a laminated structure in which a first support sheet (Y1) and a layer (X1) of the first curable resin (X1) are laminated is pressed against and bonded to the bump formation surface of the semiconductor chip production wafer with the layer (X1) as a bonding surface.
8. The method of manufacturing a semiconductor chip according to claim 7,
the process (S-BG) is included after the process (S2) and before the process (S3),
the step (S-BG) is carried out by: grinding the back surface of the wafer for manufacturing semiconductor chips while the first composite sheet (alpha 1) is bonded, and then peeling the first support sheet (Y1) from the first composite sheet (alpha 1),
the step (S4) is performed by: the first cured resin film (r1) of the semiconductor chip manufacturing wafer with the first cured resin film (r1) is cut at the portions formed in the groove portions along the lines to be divided.
9. The method for manufacturing a semiconductor chip according to claim 7,
the process (S-BG) is included after the process (S3) and before the process (S4),
the step (S3) is performed without peeling the first support sheet (Y1) from the first composite sheet (alpha 1),
the step (S-BG) is performed by: grinding the back surface of the wafer for manufacturing semiconductor chips while the first composite sheet (alpha 1) is bonded, and then peeling the first support sheet (Y1) from the first composite sheet (alpha 1),
the step (S4) is performed by: the first cured resin film (r1) of the semiconductor chip manufacturing wafer with the first cured resin film (r1) is cut at the portions formed in the groove portions along the lines to be divided.
10. The method of manufacturing a semiconductor chip according to claim 7,
the process (S-BG) is included after the process (S3) and before the process (S4),
peeling the first support sheet (Y1) from the first composite sheet (α 1) after the process (S2) and before the process (S3),
the step (S-BG) is carried out by: attaching a back grinding sheet (b-BG) to a surface of the first cured resin film (r1) of the semiconductor chip production wafer with the first cured resin film (r1), grinding the back surface of the semiconductor chip production wafer in a state where the back grinding sheet (b-BG) is attached, and then peeling the back grinding sheet (b-BG) from the semiconductor chip production wafer with the first cured resin film (r1),
the step (S4) is performed by: the first cured resin film (r1) of the semiconductor chip manufacturing wafer with the first cured resin film (r1) is cut at the portions formed in the groove portions along the lines to be divided.
11. The method of manufacturing a semiconductor chip according to claim 7,
the step (S4) includes the step (S-BG),
peeling the first support sheet (Y1) from the first composite sheet (α 1) after the process (S2) and before the process (S3),
the step (S4) is performed by: and cutting a part of the first cured resin film (r1) of the semiconductor chip production wafer with the first cured resin film (r1), which part is formed in the groove part, into a cut along the planned dividing line, or after forming a modified region along the planned dividing line, attaching a back grinding sheet (b-BG) to a surface of the first cured resin film (r1) of the semiconductor chip production wafer with the first cured resin film (r1) as the step (S-BG), and grinding the back surface of the semiconductor chip production wafer while the back grinding sheet (b-BG) is attached.
12. The method for manufacturing a semiconductor chip according to any one of claims 6 to 11, further comprising a step (T),
step (T): and a step of forming a second cured resin film (r2) on the back surface of the wafer for manufacturing semiconductor chips.
13. The method for manufacturing a semiconductor chip according to any one of claims 6 to 12, wherein the width of the groove portion is 10 μm to 2000 μm.
14. The method for manufacturing a semiconductor chip according to any one of claims 6 to 13, wherein the depth of the groove portion is 30 μm to 700 μm.
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