CN115244654A - Protective film forming sheet - Google Patents

Protective film forming sheet Download PDF

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Publication number
CN115244654A
CN115244654A CN202180020576.2A CN202180020576A CN115244654A CN 115244654 A CN115244654 A CN 115244654A CN 202180020576 A CN202180020576 A CN 202180020576A CN 115244654 A CN115244654 A CN 115244654A
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Prior art keywords
protective film
bump
meth
acrylate
bumps
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Inventor
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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    • 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
    • H01L23/293—Organic, e.g. plastic
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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 at least one potential-jump barrier or surface barrier, e.g. 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 at least one potential-jump barrier or surface barrier, e.g. 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
    • 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
    • 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
    • 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
    • H01L24/11—Manufacturing methods
    • 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
    • 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
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector

Abstract

The invention provides a protective film forming sheet capable of suppressing short circuit between bumps with narrowed pitch. The problem is solved by forming a protective film-forming sheet comprising: the protective film forming sheet has a laminated structure of a curable resin film (X) and a support sheet (Y), and is used for forming a protective film (X) on a bump forming surface of a semiconductor wafer which has a plurality of bumps and satisfies specific requirements indicating that the semiconductor wafer has bumps with narrowed pitches, and the protective film forming sheet satisfies the specific requirements defined by a tensile modulus E'.

Description

Protective film forming sheet
Technical Field
The present invention relates to a protective film-forming sheet.
Background
Conventionally, when a multi-pin LSI package used for an MPU, a gate array, or the like is mounted on a printed wiring board, a chip having a bump electrode (hereinafter also referred to as a "bump") formed on a connection pad portion thereof has been used as a semiconductor chip. Wherein, the flip chip mounting method is adopted as follows: these bumps are brought into face-to-face contact with the corresponding terminal portions on the chip-mounting board by a so-called face down (face down) method, and fusion/diffusion bonding is performed.
In recent years, with the reduction in size and weight, the reduction in thickness, and the improvement in functionality of electronic devices, high-density mounting is also required for built-in electronic components. In patent documents 1 to 3, in order to avoid a problem associated with high-density mounting, that is, a soft error problem in which memory contents are rewritten due to intrusion of α rays into memory cells of a semiconductor integrated circuit, a solder material with a low α -ray amount is proposed.
Documents of the prior art
Patent literature
Patent document 1: japanese patent No. 4472752
Patent document 2: japanese patent laid-open publication No. 2011-214040
Patent document 3: international publication pamphlet No. 2012/120982
Disclosure of Invention
Problems to be solved by the invention
However, as demands for high-density mounting of electronic components increase, demands for narrower pitches of bumps included in semiconductor chips also increase. However, when the pitch of the bumps of the semiconductor chip is narrowed, a new problem arises. For example, in a process of electrically connecting a semiconductor chip and a wiring substrate via ball bumps, the ball bumps are flattened and spread in a lateral direction, and the ball bumps come into contact with each other to cause a short circuit. In order to meet the demand for higher density mounting, three-dimensional high density mounting in which semiconductor packages are stacked in the height direction has also been studied, and in this case, the ball bumps are gradually crushed by the weight of the semiconductor packages, and short-circuiting may be caused.
The present inventors have conducted extensive studies in view of the above-described problems, and have developed a sheet for forming a protective film capable of suppressing the ball bumps from being squashed and spreading in the lateral direction. In addition, it is also considered that, in a semiconductor chip having pillar bumps, the pillar bumps may be brought into contact with each other by bending of the pillar bumps, or the like, to cause a short circuit. The present inventors have found that the developed sheet is also effective in solving such problems of the stud bump.
Accordingly, an object of the present invention is to provide a protective film forming sheet capable of suppressing a short circuit between bumps having a narrowed pitch.
Means for solving the problems
The present inventors have found that the above problems can be solved by the following invention.
That is, the present invention relates to the following [1] to [9].
[1] A protective film-forming sheet having a laminated structure of a curable resin film (x) and a support sheet (Y),
the protective film forming sheet is used for forming a protective film (X) on a bump forming surface of a semiconductor wafer which has a plurality of bumps and satisfies the following requirements (alpha 1) - (alpha 2).
Requirement (α 1): width of the Bump (BM) w ) The unit is 20 to 350 μm.
Requirement (α 2): the pitch (BM) of the above bumps P ) (unit: μm) and the width of the Bump (BM) w ) (unit: μm) satisfies the following formula (I).
[(BM P )/(BM w )]≤1.0····(I)
Wherein the protective film-forming sheet satisfies the following requirements (β 1) to (β 3).
Requirement (β 1): the protective film (X) formed by curing the curable resin film (X) has a tensile modulus E' (23 ℃) of 1X 10 at 23 DEG C 7 Pa～1×10 10 Pa。
Requirement (β 2): the protective film (X) formed by curing the curable resin film (X) has a tensile modulus E' (260 ℃) of 1X 10 at 260 DEG 5 Pa～1×10 8 Pa。
Requirement (β 3): a protective film (X) formed by curing the curable resin film (X) has a thickness (X) at 23 DEG C T ) (unit: μm) and the height of the Bump (BM) h ) (unit: μm) satisfies the following formula (II).
[(X T )/(BM h )]≥0.2····(II)。
[2] The protective film-forming sheet according to [1], which further satisfies the following requirement (. Alpha.3a).
Requirement (α 3 a): height of the above Bump (BM) h ) And the width (BM) of the bump w ) Satisfies the following formula (IIIa),
0.2≤[(BM h )/(BM w )]≤1.0····(IIIa)。
[3] the protective film-forming sheet according to [1], which further satisfies the following requirement (. Alpha.3b).
Requirement (α 3 b): height of the Bump (BM) h ) And the width (BM) of the bump w ) Satisfying the following formula (IIIb),
0.5≤[(BM h )/(BM w )]≤5.0····(IIIb)。
[4] the protective film-forming sheet according to any one of [1] to [3], which further satisfies the following requirement (. Alpha.4).
Requirement (α 4): height of the Bump (BM) h ) 15-300 μm.
[5] The protective film-forming sheet according to any one of [1] to [4], wherein,
the support sheet (Y) is a back grinding tape.
[6] A method for manufacturing a semiconductor wafer with a protective film, comprising the steps (S1) to (S3),
step (S1): preparing a semiconductor wafer having a bump formation surface provided with a plurality of bumps;
step (S2): a step of bonding the protective film-forming sheet according to any one of [1] to [5] to the bump-forming surface of the semiconductor wafer while pressing the sheet with a curable resin film (x) as a bonding surface;
step (S3): a step of curing the curable resin film (X) to form a protective film (X),
wherein the semiconductor wafer prepared in the step (S1) satisfies the following requirements (alpha 1) to (alpha 2),
requirement (α 1): width of the Bump (BM) w ) The unit is 20-350 μm,
requirement (α 2): pitch (BM) of the above bumps P ) (unit: μm) and the width of the Bump (BM) w ) (unit: μm) satisfies the following formula (I),
[(BM P )/(BM w )]≤1.0····(I)。
[7] a method for manufacturing a semiconductor chip with a protective film, comprising the steps (T1) to (T2),
step (T1): a step of obtaining a semiconductor wafer with a protective film by carrying out the production method according to [6],
step (T2): and a step of singulating the semiconductor wafer with the protective film.
[8] A method for manufacturing a semiconductor package, comprising the following steps (U1) to (U2),
step (U1): a step of obtaining a semiconductor chip with a protective film by carrying out the production method according to [7],
step (U2): and electrically connecting the wiring substrate and the semiconductor chip with the protective film via the bump.
[9] The method for manufacturing a semiconductor package according to item [8], further comprising a step (U3),
step (U3): and filling an underfill material between the wiring board and the semiconductor chip with the protective film.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a protective film forming sheet capable of suppressing short-circuiting between bumps having a narrowed pitch can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view showing the structure of the protective film forming sheet of the present invention.
Fig. 2 is a schematic cross-sectional view showing an example of the structure of a protective film forming sheet according to an embodiment of the present invention.
Fig. 3 is a schematic cross-sectional view showing another example of the structure of the protective film forming sheet according to one embodiment of the present invention.
Fig. 4 is a schematic cross-sectional view showing another example of the structure of the protective film forming sheet according to one embodiment of the present invention.
Fig. 5 is a schematic cross-sectional view showing an example of a semiconductor wafer having a plurality of bumps.
Fig. 6 is a schematic cross-sectional view showing another example of a semiconductor wafer having a plurality of bumps.
FIG. 7 is a pitch (BM) for a bump P ) And width of the Bump (BM) w ) Top view of 3 bumps on a semiconductor wafer enlarged by definition.
Fig. 8 is a schematic cross-sectional view illustrating a step (S2) of a method for manufacturing a semiconductor wafer with a protective film according to an embodiment of the present invention.
Fig. 9 is a schematic cross-sectional view illustrating a step (S3) of a method for manufacturing a semiconductor wafer with a protective film according to an embodiment of the present invention.
Fig. 10 is a schematic cross-sectional view illustrating a step (U2) of a method for manufacturing a semiconductor package according to an embodiment of the present invention.
FIG. 11 is a graph showing the height of the Bump (BM) h ) (unit: μm) and a thickness (X) at 23 ℃ of a protective film (X) formed by curing the curable resin film (X) T ) A schematic cross-sectional view of the relationship of (unit: μm).
Description of the symbols
1. 1a, 1b, 1c protective film-forming sheet
X-curable resin film
x1 thermosetting resin film
X2 energy ray-curable resin film
X protective film
Y support piece
11. Base material
21. Adhesive layer
31. Intermediate layer
40. Semiconductor chip with bump
41. Semiconductor wafer
41a bump forming surface
BM bump
Semiconductor chip with CP protective film
Z-wiring board
Z1 wiring
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, "(meth) acrylic acid" means both "acrylic acid" and "methacrylic acid", and other similar terms are used as well.
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, for a preferable numerical range (for example, a range of a content or the like), a lower limit value and an upper limit value described in steps may be independently combined. For example, according to the description of "preferably 10 to 90, more preferably 30 to 60", the combination of "preferred lower limit value (10)" and "more preferred upper limit value (60)" can give "10 to 60".
[ mode for sheet for Forming protective film ]
The protective film forming sheet of the present invention has a laminated structure of a curable resin film (x) and a support sheet (Y).
The protective film forming sheet of the present invention is used for forming a protective film (X) on a bump forming surface of a semiconductor wafer having a plurality of bumps and satisfying the following requirements (alpha 1) to (alpha 2).
Requirement (α 1): width of the Bump (BM) w ) The unit is 20 to 350 μm.
Requirement (α 2): pitch (BM) of the above bumps P ) (unit: μm) and the width of the Bump (BM) w ) (unit: μm) satisfies the following formula (I).
[(BM P )/(BM w )]≤1.0····(I)
The protective film-forming sheet of the present invention satisfies the following requirements (β 1) to (β 3).
Requirement (β 1): the protective film (X) formed by curing the curable resin film (X) has a tensile modulus E' (23 ℃) of 1X 10 at 23 DEG C 7 Pa～1×10 10 Pa。
Requirement (β 2): the protective film (X) formed by curing the curable resin film (X) has a tensile modulus E' (260 ℃) of 1X 10 at 260 DEG 5 Pa～1×10 8 Pa。
Requirement (β 3): a protective film (X) formed by curing the curable resin film (X) has a thickness (X) at 23 DEG C T ) (unit: μm) and the height of the Bump (BM) h ) (unit: μm) satisfies the following formula (II).
[(X T )/(BM h )]≥0.2····(II)
That is, the protective film forming sheet of the present invention is used for a bump forming surface of a semiconductor wafer having bumps with a narrowed pitch, which satisfies the above requirements (α 1) to (α 2). The protective film forming sheet of the present invention has a specific structure of a laminated structure of a curable resin film (x) and a support sheet (Y), and satisfies the above requirements (β 1) to (β 3) for the curable resin film (x).
The present inventors have found that by using a protective film-forming sheet having a laminated structure of a curable resin film (X) and a support sheet (Y) and satisfying the requirements (β 1) to (β 3) for the curable resin film (X), a protective film (X) is formed on a bump-forming surface of a semiconductor wafer having bumps with a narrowed pitch satisfying the requirements (α 1) to (α 2), so that it is possible to suppress the bumps from being flattened and deformed and to suppress short-circuiting between the bumps with a narrowed pitch.
The above-mentioned requirements (β 1) to (β 3) relating to the protective film (X) defined in the protective film forming sheet of the present invention will be described below.
< requirement (. Beta.1) >)
The requirement (. Beta.1) defines that the tensile modulus E' (23 ℃) at 23 ℃ of a protective film (X) formed by curing a curable resin film (X) is 1X 10 7 Pa～1×10 10 Pa。
A tensile modulus E' (23 ℃) of less than 1X 10 7 At Pa, the protective film (X) cannot suppress the bumps from being flattened or deformed, and there is a risk that the bumps come into contact with each other to cause short-circuiting.
On the other hand, the tensile modulus E' (23 ℃ C.) exceeds 1X 10 10 When Pa, the stress increases during heating and cooling, and a load is applied to the bump, thereby lowering the reliability.
Here, the tensile modulus E' (23 ℃) of the protective film (X) formed by curing the curable resin film (X) at 23 ℃ is preferably 3 × 10 from the viewpoint of more easily suppressing the collapse and deformation of the bump and suppressing the load applied to the bump at the time of heating and cooling 7 Pa～8×10 9 Pa, more preferably 5X 10 7 Pa～7×10 9 Pa, more preferably 7X 10 7 Pa～6×10 9 Pa。
The protective film (X) having the tensile modulus E' (23 ℃) defined by the requirement (β 1) can be formed by curing the curable resin film (X). The method for producing the curable resin film (X) for forming the protective film (X) is as described later.
< requirement (. Beta.2) >)
The requirement (. Beta.2) is that the tensile modulus E' (260 ℃) of a protective film (X) formed by curing a curable resin film (X) at 260 ℃ is 1X 10 5 Pa～1×10 8 Pa。
A tensile modulus E' (260 ℃) of less than 1X 10 5 Pa, in particular, a heating temperature range in a step of electrically connecting the wiring board and the semiconductor wafer having the bump via the bump: (For example, at 250 ℃ to 270 ℃), the protective film (X) cannot suppress the bumps from being crushed and deformed, and there is a risk that the bumps come into contact with each other and short-circuiting occurs.
On the other hand, the tensile modulus E' (260 ℃ C.) exceeds 1X 10 8 At Pa, the stress increases during heating and cooling, and a load is applied to the bump, thereby reducing reliability and bondability.
Here, the tensile modulus E' (260 ℃) of the protective film (X) formed by curing the curable resin film (X) at 260 ℃ is preferably 7 × 10 from the viewpoint of more easily suppressing the collapse and deformation of the bump and suppressing the load applied to the bump at the time of heating and cooling 5 Pa～3×10 7 Pa, more preferably 9X 10 5 Pa～2×10 7 Pa, more preferably 1X 10 6 Pa～1.5×10 7 Pa。
The protective film (X) having the tensile modulus E' (260 ℃) defined by the requirement (β 2) can be formed by curing the curable resin film (X). The method for producing the curable resin film (X) for forming the protective film (X) is as described later.
< requirement (. Beta.3) >)
The requirement (. Beta.3) defines the thickness (X) of a protective film (X) formed by curing a curable resin film (X) at 23 DEG C T ) (unit: μm) and the height of the Bump (BM) h ) (unit: μm). Specifically, the following formula (II) is satisfied.
[(X T )/(BM h )]≥0.2····(II)
[(X T )/(BM h )]If < 0.2, the coating height of the protective film (X) is equal to the height of the Bump (BM) h ) The protective film (X) cannot suppress the bumps from being flattened or deformed, and the bumps may contact each other to cause a short circuit.
Note that [ (X) T )/(BM h )]The upper limit of (b) is not particularly limited, but is preferably 1.0 or less, and more preferably less than 1.0, from the viewpoint of exposing the top of the bump from the protective film (X).
Here, from the viewpoint of more easily suppressing the collapse and deformation of the bump and the viewpoint of exposing the top of the bump from the protective film (X), the requirement (β 3) preferably satisfies the following formula (IIa).
P≤[(X T )/(BM h )]≤Q····(IIa)
In the formula (IIa), P is 0.2, preferably 0.30, more preferably 0.40, and further preferably 0.50.
In formula (IIa), Q is preferably 1.0, more preferably 0.90, and still more preferably 0.80.
The thickness of the curable resin film (X) satisfying the relationship defined by the requirement (β 3) can be adjusted based on information such as the relationship between the thickness of the curable resin film (X) and the thickness of the protective film (X) formed by curing the curable resin film (X), and the height of the bump included in the semiconductor wafer to be used.
The height of the Bump (BM) is shown in FIG. 11 h ) (unit: μm) and a thickness (X) at 23 ℃ of a protective film (X) formed by curing the curable resin film (X) T ) (unit: μm).
As shown in FIG. 11, the thickness (X) of the protective film (X) formed by curing the curable resin film (X) is 23 DEG C T ) (unit: μm) means that the bump height (BM) was measured with a focus on h ) The height of the bump (bump BM) from the bump formation surface 41a at a position 50 farthest from the bump formation surface 41a in the contact portion between the bump and the protective film (X).
Wherein the position 50 farthest from the bump forming surface 41a is determined in a region where the protective film (X) formed on the bump forming surface 41a continuously exists. Therefore, for example, the position 50 farthest from the bump formation surface 41a is not determined from the contact portion between the bump and the protective film (X) which is locally present on the top of the bump and is removed by an exposure process (plasma etching process) described later. In addition, when the exposure treatment (plasma etching treatment) described later is performed, the thickness of the protective film (X) formed by the exposure treatment after the recession needs to satisfy the above formula (II) (0.2 μm or more). That is, the thickness of the protective film (X) is required to satisfy the above formula (II) (to be 0.2 μm or more) immediately before the step of electrically connecting the semiconductor chip and the wiring substrate via the ball bump, regardless of the presence or absence of exposure treatment described later.
Height of Bump (BM) h ) And thickness (X) of the protective film (X) T ) This can be determined, for example, in the following manner: the semiconductor wafer with the protective film (X) is cut in a direction perpendicular to a bump formation surface and passing through the center of the bump, and the cut section is observed by an optical microscope.
Hereinafter, the protective film forming sheet of the present invention will be described in detail based on a method for producing a curable resin film (X) for forming a protective film (X) satisfying the requirement (β 1) and the requirement (β 2).
Constitution of sheet for Forming protective film
Fig. 1 shows an example of the structure of the protective film-forming sheet of the present invention.
The protective film forming sheet according to one embodiment of the present invention includes a curable resin film (x) on one surface of a support sheet (Y) as in the protective film forming sheet 1 shown in fig. 1. By providing the curable resin film (x) on one surface of the support sheet (Y), the curable resin film (x) is stably supported and protected when the curable resin film (x) is conveyed as a product package and conveyed in the process.
Fig. 2 to 4 show examples of the structure of the protective film forming sheet according to one embodiment of the present invention.
As shown in the protective film-forming sheet 1a shown in fig. 2, the protective film-forming sheet according to one embodiment of the present invention has a support sheet (Y) as a base material 11, and a curable resin film (x) on one surface of the base material 11.
In addition, as in the protective film forming sheet 1b shown in fig. 3, the support sheet (Y) is an adhesive sheet in which the substrate 11 and the adhesive layer 21 are laminated, and the adhesive layer 21 of the adhesive sheet and the curable resin film (x) can be bonded together.
In addition, as in the protective film forming sheet 1c shown in fig. 4, the support sheet (Y) is an adhesive sheet in which the substrate 11, the intermediate layer 31, and the adhesive layer 21 are laminated in this order, and the adhesive layer 21 of the adhesive sheet and the curable resin film (x) can be bonded together. The pressure-sensitive adhesive sheet in which the substrate 11, the intermediate layer 31, and the pressure-sensitive adhesive layer 21 are laminated in this order can be suitably used as a back-grinding tape. That is, since the protective film forming sheet 1c shown in fig. 4 has a back grinding tape as the support sheet (Y), it can be suitably used when the semiconductor wafer is thinned by grinding one surface of the semiconductor wafer opposite to the bump forming surface (hereinafter also referred to as "back surface of the semiconductor wafer") after the curable resin film (x) of the protective film forming sheet 1c is bonded to the bump forming surface of the semiconductor wafer having a plurality of bumps.
The curable resin film (x) and the support sheet (Y) used in the protective film-forming sheet of the present invention will be described below.
Curable resin Membrane (x) of the book
The curable resin film (X) is a film for protecting a bump formation surface of a semiconductor wafer having a plurality of bumps, and the protective film (X) is formed by curing by heating or energy ray irradiation. That is, the curable resin film (x) may be a thermosetting resin film (x 1) cured by heating, or may be an energy ray curable resin film (x 2) cured by irradiation of an energy ray.
In the present specification, the term "energy beam" refers to a beam having an energy quantum in an electromagnetic wave or a charged particle beam. Examples thereof include ultraviolet rays and electron beams, and preferable examples thereof include ultraviolet rays.
The physical properties of the curable resin film (x) can be adjusted by adjusting either or both of the type and amount of the components contained in the curable resin film (x).
The thermosetting resin film (x 1) and the energy ray-curable resin film (x 2) will be described below.
< thermosetting resin film (x 1) >)
The thermosetting resin film (x 1) contains a polymer component (a) and a thermosetting component (B).
The thermosetting resin film (x 1) is formed from, for example, a thermosetting resin composition (x 1-1) containing a polymer component (a) and a thermosetting component (B).
The polymer component (a) can be considered to be a component formed by a polymerization reaction of a polymerizable compound. The thermosetting component (B) is a component capable of undergoing a curing (polymerization) reaction using heat as a trigger of the reaction. The curing (polymerization) reaction also includes a polycondensation reaction.
In the following description of the present specification, the "content of each component in the total amount of the active components of the thermosetting resin composition (x 1-1)" is the same as the "content of each component of the thermosetting resin film (x 1) formed from the thermosetting resin composition (x 1-1)".
(Polymer component (A))
The thermosetting resin film (x 1) and the thermosetting resin composition (x 1-1) mean the polymer component (A).
The polymer component (a) is a polymer compound for imparting film formability, flexibility, and the like to the thermosetting resin film (x 1). The polymer component (A) may be used alone in 1 kind, or may be used in combination of 2 or more kinds. When 2 or more polymer components (a) are used in combination, the combination and ratio thereof can be arbitrarily selected.
Examples of the polymer component (a) include: polyvinyl acetal, acrylic resins (resins having a (meth) acryloyl group), polyesters, urethane resins (resins having a urethane bond), acrylic urethane resins, silicone resins (resins having a siloxane bond), rubber resins (resins having a rubber structure), phenoxy resins, and thermosetting polyimides. These may be used alone in 1 kind, or in combination of 2 or more kinds.
Among them, 1 or more selected from polyvinyl acetal and acrylic resin is preferable.
Hereinafter, polyvinyl acetal and an acrylic resin which are preferable as the polymer component (a) will be described as examples.
Polyvinyl Acetal
The polyvinyl acetal used as the polymer component (a) is not particularly limited, and for example, known polyvinyl acetal can be used.
Among the polyvinyl acetals, mention may be made, for example, of: polyvinyl formal, polyvinyl butyral, and the like, and more preferably polyvinyl butyral.
The polyvinyl butyral preferably has structural units represented by the following formulae (i-1), (i-2) and (i-3) from the viewpoint of improving adhesion between the bump forming surface of the semiconductor wafer and the protective film (X).
[ chemical formula 1]
Figure BDA0003840839940000111
In the above formulae (i-1), (i-2) and (i-3), p, q and r are the content ratios (mol%) of the respective structural units.
The weight average molecular weight (Mw) of the polyvinyl acetal is preferably 5000 to 200000, more preferably 8000 to 100000, further preferably 9000 to 80000, and further preferably 10000 to 50000. When the weight average molecular weight of the polyvinyl acetal is in such a range, the adhesion between the bump formation surface of the semiconductor wafer and the protective film (X) can be easily improved. In addition, the effect of suppressing the residual of the protective film (X) on the upper portion of the bump (the top portion of the bump and the vicinity thereof) is further improved.
The content ratio p (butyralation degree) of the structural unit of the butyraldehyde group represented by the formula (i-1) is preferably 40 to 90 mol%, more preferably 50 to 85 mol%, and still more preferably 60 to 76 mol%, based on the total structural units of the polymer component (a).
The content q of the structural unit having an acetyl group represented by the above formula (i-2) is preferably 0.1 to 9 mol%, more preferably 0.5 to 8 mol%, and still more preferably 1 to 7 mol%, based on the entire structural units of the polymer component (a).
The content ratio r of the structural unit having a hydroxyl group represented by the above formula (i-3) is preferably 10 to 60 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol%, based on the whole structural units of the polymer component (a).
The glass transition temperature (Tg) of the polyvinyl acetal is preferably from 40 to 80 ℃ and more preferably from 50 to 70 ℃. When the Tg of the polyvinyl acetal is in such a range, the effect of suppressing the protective film (X) from remaining on the upper portion of the bump is further improved when the thermosetting resin film (X1) is attached to the bump formation surface of the bumped wafer, and the hardness of the protective film formed by thermosetting the thermosetting resin layer can be made sufficient.
In the present specification, the glass transition temperature (Tg) of the polymer (resin) is a value measured by the method described in examples as described below.
The content ratio of the 3 kinds of structural units constituting the polyvinyl butyral can be arbitrarily adjusted depending on the desired physical properties.
The polyvinyl butyral may have a structural unit other than the 3 kinds of structural units, and the content of the 3 kinds of structural units is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, and further preferably 100 mol% based on the total amount of the polyvinyl butyral.
Acrylic resin
Examples of the acrylic resin include known acrylic polymers.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10000 to 2000000, more preferably 100000 to 1500000.
By setting the weight average molecular weight of the acrylic resin to be not less than the lower limit, the shape stability (stability with time during storage) of the thermosetting resin film (x 1) can be easily improved. Further, by setting the weight average molecular weight of the acrylic resin to the upper limit value or less, the solid resin film (x 1) is easily allowed to follow the uneven surface of the heat-adhered object, and generation of a void or the like between the heat-adhered object and the thermosetting resin film (x 1) is easily suppressed, for example.
The glass transition temperature (Tg) of the acrylic resin is preferably from-60 to 70 ℃, more preferably from-30 to 50 ℃.
When the glass transition temperature (Tg) of the acrylic resin is not lower than the lower limit value, the adhesion between the protective film (X) and the support sheet (Y) is suppressed, and the peelability of the support sheet (Y) is improved. When the glass transition temperature (Tg) of the acrylic resin is not higher than the upper limit value, the adhesive strength of the adherend between the thermosetting resin film (X1) and the protective film (X) is improved.
Examples of the acrylic resin include: one or two or more polymers of (meth) acrylic acid esters; and copolymers of two or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide.
Examples of the (meth) acrylate constituting the acrylic resin include: alkyl (meth) acrylates having a chain structure in which an alkyl group constituting an alkyl ester is a carbon number of 1 to 18, such as 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), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, palmityl (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;
cycloalkoxyalkyl (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.
In the present specification, 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 be obtained by copolymerizing 1 or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylol acrylamide, for example, in addition to (meth) acrylate.
The acrylic resin may be composed of 1 monomer or 2 or more monomers. When the number of the monomers constituting the acrylic resin is 2 or more, the combination and ratio thereof can be arbitrarily selected.
The acrylic resin may have a functional group capable of bonding to another compound, such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, and 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 via the crosslinking agent (F). By bonding the acrylic resin and another compound using the functional group, the reliability of the package obtained using the thermosetting resin film (x 1) tends to be improved.
Other resins
In one embodiment of the present invention, the polyvinyl acetal and the thermoplastic resin other than the acrylic resin (hereinafter, may be simply referred to as "thermoplastic resin") may be used alone without using the acrylic resin as the polymer component (a), or the polyvinyl acetal and/or the acrylic resin may be used in combination.
By using the thermoplastic resin, the releasability of the protective film (X) from the support sheet (Y) is improved, the thermosetting resin film (X1) is likely to follow the uneven surface of the adherend, and the occurrence of a void or the like between the adherend and the thermosetting resin film (X1) is suppressed in some cases.
The weight average molecular weight of the thermoplastic resin is preferably 1000 to 100000, more preferably 3000 to 80000.
The glass transition temperature (Tg) of the thermoplastic resin is preferably-30 to 150 ℃, more preferably-20 to 120 ℃.
Examples of the thermoplastic resin include: polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, and the like.
The thermoplastic resin can be used alone in 1, can also be combined with more than 2. When the thermoplastic resin is 2 or more, the combination and ratio thereof can be arbitrarily selected.
Content of Polymer component (A)
From the viewpoint of easily obtaining the protective film (X) satisfying the requirement (β 1) and the requirement (β 2), the content of the polymer component (a) is preferably 5 to 85 mass%, more preferably 10 to 80 mass%, further preferably 15 to 70 mass%, further preferably 15 to 60 mass%, and further preferably 15 to 50 mass%, based on the total amount of the active ingredients of the thermosetting resin composition (X1-1).
Preferred modes of Polymer component (A)
As described above, the polymer component (a) is preferably 1 or more selected from polyvinyl acetal and an acrylic resin, and the polymer component (a) is preferably polyvinyl acetal from the viewpoint of more easily obtaining the protective film (X) satisfying the requirement (β 1) and the requirement (β 2).
The polymer component (a) may be a thermosetting component (B). In the present invention, when the thermosetting resin composition (x 1-1) contains such components belonging to both the polymer component (a) and the thermosetting component (B), the thermosetting resin composition (x 1-1) is considered to contain both the polymer component (a) and the thermosetting component (B).
(thermosetting component (B))
The thermosetting resin film (x 1) and the thermosetting resin composition (x 1-1) contain a thermosetting component (B).
The thermosetting component (B) is a component for curing the thermosetting resin film (X1) to form a hard protective film (X).
The thermosetting component (B) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When the thermosetting component (B) is 2 or more, the combination and ratio thereof can be arbitrarily selected.
Examples of the thermosetting component (B) include: epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, and the like. Among these, epoxy thermosetting resins are preferable.
The epoxy thermosetting resin contains an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy thermosetting resin may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When the epoxy thermosetting resin is 2 or more, the combination and ratio thereof can be arbitrarily selected.
Epoxy resin (B1)
Examples of the epoxy resin (B1) include known epoxy resins, and examples thereof include: polyfunctional epoxy resins, biphenyl compounds, bisphenol a diglycidyl ether and hydrogenated products thereof, o-cresol novolac epoxy resins, dicyclopentadiene epoxy resins, biphenyl epoxy resins, bisphenol a epoxy resins, bisphenol F epoxy resins, phenylene skeleton epoxy resins, and the like, and bifunctional or more epoxy compounds.
As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group may also be used. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, by using the epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the thermosetting resin film (x 1) is 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 with an epoxy group. Examples of the epoxy resin having an unsaturated hydrocarbon group include: and compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting an epoxy resin.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include vinyl group (vinyl group, ethyl group), 2-propenyl group (allyl group), (meth) acryloyl group, and (meth) acrylamide group. Among them, an acryloyl group is preferable.
The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30000, more preferably 400 to 10000, and further preferably 500 to 3000, from the viewpoints of curability of the thermosetting resin film (X1), and strength and heat resistance of the protective film (X) after curing.
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000g/eq, more preferably 300 to 800g/eq.
The epoxy resin (B1) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When 2 or more epoxy resins (B1) are used in combination, the combination and ratio thereof can be arbitrarily selected.
Thermosetting agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
Examples of the thermosetting agent (B2) include: a compound having 2 or more functional groups capable of reacting with an epoxy group in 1 molecule. Examples of the functional group include: and a group in which a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid group are formed into an anhydride, and the like, a group in which a phenolic hydroxyl group, an amino group, or an acid group is formed into an anhydride is preferable, and a phenolic hydroxyl group or an amino group is more preferable.
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, and aralkyl phenol resins.
Examples of the amine-based curing agent having an amino group in the thermosetting agent (B2) include: dicyandiamide (hereinafter, also simply referred to as "DICY") and the like.
The heat-curing agent (B2) may be a heat-curing agent having an unsaturated hydrocarbon group.
Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group 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 an 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.
When a phenol curing agent is used as the thermosetting agent (B2), the thermosetting agent (B2) is preferably a thermosetting agent having a high softening point or glass transition temperature in terms of easily improving the peelability of the protective film (X) from the support sheet (Y).
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 30000, more preferably 400 to 10000, and still more preferably 500 to 3000.
The molecular weight of the non-resin component in the thermosetting agent (B2), such as biphenol and dicyandiamide, is not particularly limited, but is preferably 60 to 500, for example.
The thermosetting agent (B2) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When the number of the thermosetting agent (B2) is 2 or more, the combination and ratio thereof can be arbitrarily selected.
In the thermosetting resin composition (x 1-1), the content of the thermosetting resin (B2) is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, relative to 100 parts by mass of the content of the epoxy resin (B1). When the content of the thermosetting agent (B2) is not less than the lower limit value, the thermosetting resin film (x 1) can be cured more easily. Further, when the content of the thermosetting agent (B2) is not more than the above upper limit, the moisture absorption rate of the thermosetting resin film (x 1) is reduced, and the reliability of the package obtained using the thermosetting resin film (x 1) is further improved.
In the thermosetting resin composition (x 1-1), the content of the thermosetting component (B) (the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is preferably 50 to 1000 parts by mass, more preferably 70 to 800 parts by mass, further preferably 80 to 600 parts by mass, further preferably 90 to 500 parts by mass, and further preferably 100 to 400 parts by mass, relative to 100 parts by mass of the content of the polymer component (a). When the content of the thermosetting component (B) is in such a range, the adhesion between the protective film (X) and the support sheet (Y) is suppressed, and the peelability of the support sheet (Y) is improved. Further, the protective film (X) satisfying the requirement (β 1) and the requirement (β 2) can be easily obtained. The tensile modulus E' tends to be increased as the amount of the thermosetting component (B) relative to the polymer component (a) is increased. Conversely, the tensile modulus E' tends to decrease as the amount of the thermosetting component (B) relative to the polymer component (a) decreases.
(curing Accelerator (C))
The thermosetting resin film (x 1) and the thermosetting resin composition (x 1-1) may contain a curing accelerator (C).
The curing accelerator (C) is a component for adjusting the curing rate of the thermosetting resin composition (x 1-1).
Preferred examples of the curing accelerator (C) include: tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; 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; organic phosphines (phosphine in which 1 or more hydrogen atoms are substituted with an organic group), such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenyl radical
Figure BDA0003840839940000171
Tetraphenylborate such as tetraphenylborate and triphenylphosphine tetraphenylborate.
The curing accelerator (C) may be used alone in 1 kind, or may be used in combination of 2 or more kinds. When the number of the curing accelerator (C) is 2 or more, the combination and ratio thereof can be arbitrarily selected.
In the thermosetting resin composition (x 1-1), the content of the curing accelerator (C) when the curing accelerator (C) is used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the content of the thermosetting component (B). By setting the content of the curing accelerator (C) to the lower limit value or more, the effect of using the curing accelerator (C) can be more remarkably obtained. Further, by setting the content of the curing accelerator (C) to the above upper limit or less, for example, the effect of suppressing the migration and segregation of the highly polar curing accelerator (C) toward the adhesion interface side with the adherend in the thermosetting resin film (x 1) under high temperature/high humidity conditions is increased, and the reliability of the package obtained using the thermosetting resin film (x 1) is further improved.
(Filler (D))
The thermosetting resin film (x 1) and the thermosetting resin composition (x 1-1) may contain a filler (D).
By containing the filler (D), the thermal expansion coefficient of the protective film (X) obtained by curing the curable resin film (X1) can be easily adjusted to an appropriate range, and the reliability of the package obtained using the thermosetting resin film (X1) can be further improved. In addition, by incorporating the filler (D) into the thermosetting resin film (X1), the moisture absorption rate of the protective film (X) can be reduced, and the heat dissipation properties can be improved.
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, iron oxide red, silicon carbide, boron nitride, and the like; forming the inorganic filler into spherical beads; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic filler materials; glass fibers, and the like.
The filler (D) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
When the number of the filler (D) is 2 or more, the combination and ratio thereof can be arbitrarily selected.
When the filler (D) is used, the content of the filler (D) is preferably 5 to 80% by mass, more preferably 7 to 60% by mass, based on the total amount of the active ingredients of the thermosetting resin composition (x 1-1). By setting the content of the filler (D) in such a range, the adjustment of the thermal expansion coefficient can be performed more easily.
The average particle diameter of the filler (D) is preferably 5 to 1000nm, more preferably 5 to 500nm, and still more preferably 10 to 300nm. The average particle size is obtained by measuring the outer diameter of 1 particle at a plurality of sites and averaging the measured outer diameters.
(coupling agent (E))
The thermosetting resin film (x 1) and the thermosetting resin composition (x 1-1) may contain a coupling agent (E).
By using a coupling agent 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 thermosetting resin film (x 1) to the adherend can be easily improved. In addition, the protective film (X) obtained by curing the thermosetting resin film (X1) using the coupling agent (E) does not impair heat resistance, and is easy to improve water resistance.
The coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional groups of the polymer component (a), the thermosetting component (B), and the like, and more preferably a silane coupling agent. Preferred silane coupling agents include, for example: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxymethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane and the like.
The coupling agent (E) may be used alone in 1 kind, or may be used in combination of 2 or more kinds. When the number of the coupling agents (E) is 2 or more, their combination and ratio can be arbitrarily selected.
In the thermosetting resin composition (x 1-1), the content of the coupling agent (E) when the coupling agent (E) is used is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and still more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total content of the polymer component (a) and the thermosetting component (B). By setting the content of the coupling agent (E) to the lower limit value or more, effects of using the coupling agent (E) such as improvement of dispersibility of the filler (D) in the resin, improvement of adhesiveness between the thermosetting resin film (x 1) and the adherend, and the like can be more remarkably obtained. Further, by setting the content of the coupling agent (E) to the above-described upper limit or less, the occurrence of outgassing (outgas) can be further suppressed.
(crosslinking agent (F))
When the polymer component (a) is a component having a functional group such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group or isocyanate group which can be bonded to another compound, such as the acrylic resin described above, the thermosetting resin film (x 1) and the thermosetting resin composition (x 1-1) may contain a crosslinking agent (F) for bonding the functional group to another compound to crosslink the resin.
The initial adhesion and cohesion of the thermosetting resin film (x 1) can be adjusted by crosslinking with the crosslinking agent (F).
Examples of the crosslinking agent (F) include: an organic polyisocyanate compound, an organic polyimine 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 such as the aromatic polyisocyanate compounds; isocyanate-terminated urethane prepolymers obtained by reacting the above aromatic polyisocyanate compounds and the like with polyol compounds, and the like. The "adduct" is 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, and examples thereof include xylylene diisocyanate adduct of trimethylolpropane.
As the organic polyisocyanate compound, more specifically, for example, there can be mentioned: 2, 4-toluene diisocyanate; 2, 6-toluene diisocyanate; 1, 3-xylylene diisocyanate; 1, 4-xylene 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 toluene 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 polyimine compound include: n, N ' -diphenylmethane-4, 4' -bis (1-aziridinecarboxamide), trimethylolpropane-tris- β -aziridinylpropionate, tetramethylolmethane-tris- β -aziridinylpropionate, and N, N ' -toluene-2, 4-bis (1-aziridinecarboxamide) triethylenemelamine.
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 thermosetting resin film (x 1) by the reaction of the crosslinking agent (F) with the polymer component (a).
The crosslinking agent (F) may be used alone in 1 kind, or may be used in combination of 2 or more kinds. When the number of the crosslinking agents (F) is 2 or more, their combination and ratio can be arbitrarily selected.
In the thermosetting resin composition (x 1-1), the content of the crosslinking agent (F) when the crosslinking agent (F) is used is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 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. Further, by setting the content of the crosslinking agent (F) to the upper limit or less, the excessive use of the crosslinking agent (F) can be suppressed.
(energy ray-curable resin (G))
The thermosetting resin film (x 1) and the thermosetting resin composition (x 1-1) may contain the energy ray-curable resin (G).
The thermosetting resin film (x 1) contains the energy ray-curable resin (G), and thus can change its properties upon irradiation with energy rays.
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: the compound having at least 1 polymerizable double bond in the molecule is preferably an acrylate compound having a (meth) acryloyl group.
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 dicyclopentanyl 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 30000, more preferably 300 to 10000.
The energy ray-curable compound used for the polymerization may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When the number of the energy ray-curable compounds used for the polymerization is 2 or more, the combination and ratio thereof can be arbitrarily selected.
The content of the energy ray-curable resin (G) when the energy ray-curable resin (G) is used 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 thermosetting resin composition (x 1-1).
(photopolymerization initiator (H))
When the thermosetting resin film (x 1) and the thermosetting resin composition (x 1-1) contain the energy ray-curable resin (G), the thermosetting resin film (x 1) and the thermosetting resin composition (x 1-1) may contain a photopolymerization initiator (H) in order to efficiently perform a polymerization reaction of the energy ray-curable resin (G).
Specific examples of the photopolymerization initiator (H) include: benzophenone, acetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoylbenzoic acid methyl ester, benzoin dimethyl ether, 2, 4-diethyl thiazolone, 1-hydroxycyclohexyl phenyl ketone, benzyl diphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzil, bibenzyl, butanedione, 1, 2-diphenylmethane, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, and 2-chloroanthraquinone, and the like.
The photopolymerization initiator (H) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When the number of photopolymerization initiators (H) is 2 or more, the combination and ratio thereof can be arbitrarily selected.
In the thermosetting resin composition (x 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).
(general additive (I))
The thermosetting resin film (x 1) and the thermosetting resin composition (x 1-1) may contain a general-purpose additive (I) within a range not to impair the effects of the present invention. The general-purpose additive (I) may be any known additive, and may be selected arbitrarily according to the purpose, and is not particularly limited.
Preferred general additives (I) include, for example: plasticizers, antistatic agents, antioxidants, colorants (dyes, pigments), getters, and the like.
The general-purpose additive (I) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. In the case where the number of the general-purpose additives (I) is 2 or more, their combination and ratio can be arbitrarily selected.
The content of the general-purpose additive (I) is not particularly limited and may be appropriately selected depending on the purpose.
(solvent)
The thermosetting resin composition (x 1-1) preferably further contains a solvent.
The thermosetting resin composition (x 1-1) containing a solvent is excellent in handling properties.
The solvent is not particularly limited, and preferable solvents include, for example: 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 can be used alone in 1, can also be combined with more than 2. When the number of the solvents is 2 or more, the combination and ratio thereof can be arbitrarily selected.
The solvent is preferably methyl ethyl ketone or the like from the viewpoint of being able to more uniformly mix the components contained in the thermosetting resin composition (x 1-1).
(method for producing thermosetting resin composition (x 1-1))
The thermosetting resin composition (x 1-1) can be prepared by compounding the respective components constituting it.
The order of addition of the components is not particularly limited, and two or more components may be added simultaneously. When a solvent is used, the solvent may be mixed with any compounding ingredient other than the solvent to dilute the compounding ingredient in advance and then used, or the solvent may be mixed with any compounding ingredient other than the solvent without diluting the compounding ingredient in advance and used.
The method of mixing the components at the time of blending is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer, a paddle, and the like, a method of mixing using a mixer, and a method of mixing by applying ultrasonic waves.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each component is not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ℃.
< energy ray-curable resin film (x 2) >)
The energy ray-curable resin film (x 2) contains an energy ray-curable component (a).
The energy ray-curable resin film (x 2) is formed from, for example, an energy ray-curable resin composition (x 2-1) containing an energy ray-curable component (a).
The energy ray-curable component (a) is preferably uncured, preferably adhesive, and more preferably uncured and adhesive.
In the following description of the present specification, the "content of each component based on the total amount of active ingredients of the energy ray-curable resin composition (x 2-1)" is the same as the "content of each component of the energy ray-curable resin film (x 2) formed from the energy ray-curable resin composition (x 2-1)".
(energy ray-curable component (a))
The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component for imparting film formability, flexibility, and the like to the energy ray-curable resin film (x 2).
Examples of the energy ray-curable component (a) include: a polymer (a 1) having an energy ray-curable group and a weight-average molecular weight of 80000 to 2000000, and a compound (a 2) having an energy ray-curable group and a molecular weight of 100 to 80000. The polymer (a 1) may be a polymer at least a part of which is crosslinked by a crosslinking agent, or may be an uncrosslinked polymer.
(Polymer (a 1))
Examples of the polymer (a 1) having an energy ray-curable group and a weight average molecular weight of 80000 to 2000000 include an acrylic resin (a 1-1) obtained by polymerizing an acrylic polymer (a 11) and an energy ray-curable compound (a 12), the acrylic polymer (a 11) having a functional group capable of reacting with a group of another compound, and the energy ray-curable compound (a 12) having an energy ray-curable group such as a group capable of reacting with the functional group and an energy ray-curable double bond.
Examples of the functional group capable of reacting 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, the functional group is preferably a group other than a carboxyl group from the viewpoint of preventing corrosion of circuits such as semiconductor wafers and semiconductor chips. Among them, the functional group is preferably a hydroxyl group.
Acrylic Polymer having functional group (a 11)
Examples of the acrylic polymer (a 11) having a functional group include a polymer obtained by copolymerizing an acrylic monomer having a functional group and an acrylic monomer having no functional group, and monomers other than the acrylic monomer (non-acrylic monomer) may be copolymerized in addition to these monomers. The acrylic polymer (a 11) may be a random copolymer or a block copolymer.
As the acrylic monomer having a functional group, for example: hydroxyl group-containing monomers, carboxyl group-containing monomers, amino group-containing monomers, substituted amino group-containing monomers, epoxy group-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 (unsaturated alcohols having no (meth) acryloyl skeleton) such as vinyl alcohol and allyl alcohol.
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 a 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 a functional group constituting the acrylic polymer (a 11) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When the number of the acrylic monomers having a functional group constituting the acrylic polymer (a 11) is 2 or more, the combination and ratio thereof can be arbitrarily selected.
Examples of the acrylic monomer having no functional group include: examples of the alkyl (meth) acrylate include alkyl (meth) acrylates having a chain structure in which the alkyl group constituting the alkyl ester is a carbon number of 1 to 18, such as 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), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearyl (meth) acrylate).
As the acrylic monomer having a 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 such as aryl (meth) acrylates including phenyl (meth) acrylate; non-crosslinkable (meth) acrylamide and derivatives thereof; and non-crosslinkable (meth) acrylic esters having a 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 (a 11) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When the number of the acrylic monomers having no functional group constituting the acrylic polymer (a 11) is 2 or more, the combination and ratio thereof can 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 (a 11) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When the number of the non-acrylic monomers constituting the acrylic polymer (a 11) is 2 or more, the combination and ratio thereof can be arbitrarily selected.
In the acrylic polymer (a 11), the proportion (content) of the amount of the structural unit derived from the acrylic monomer having a functional group is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and still more preferably 3 to 30% by mass, relative to the total mass of the structural units constituting the acrylic polymer. By setting the above ratio to such a range, the content of the energy ray-curable group in the acrylic resin (a 1-1) obtained by copolymerization of the acrylic polymer (a 11) and the energy ray-curable compound (a 12) can be easily adjusted to a preferable range.
The acrylic polymer (a 11) constituting the acrylic resin (a 1-1) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When the number of the acrylic polymer (a 11) constituting the acrylic resin (a 1-1) is 2 or more, the combination and ratio thereof can be arbitrarily selected.
The content of the acrylic resin (a 1-1) is preferably 1 to 60% by mass, more preferably 3 to 50% by mass, and even more preferably 5 to 40% by mass, based on the total amount of the active ingredients of the energy ray-curable resin composition (x 2-1).
Energy ray-curable Compound (a 12)
The energy ray-curable compound (a 12) preferably has 1 or 2 or more groups selected from isocyanate groups, epoxy groups and carboxyl groups as groups capable of reacting with the functional groups of the acrylic polymer (a 11), and more preferably has an isocyanate group as the groups.
When the energy ray-curable compound (a 12) has, for example, an isocyanate group as the above group, the isocyanate group is easily reacted with the hydroxyl group of the acrylic polymer (a 11) having a hydroxyl group as the above functional group.
The energy ray-curable compound (a 12) preferably has 1 to 5 energy ray-curable groups in 1 molecule, and more preferably 1 to 2.
Examples of the energy ray-curable compound (a 12) include: 2-methacryloyloxyethyl isocyanate, m-isopropenyl- α, α -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1- (bisacryloxymethyl) ethyl isocyanate; an acryloyl monoisocyanate compound obtained by the reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate; and acryloyl monoisocyanate compounds obtained by the reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth) acrylate. Among these, the energy ray-curable compound (a 12) is preferably 2-methacryloyloxyethyl isocyanate.
The energy ray-curable compound (a 12) constituting the acrylic resin (a 1-1) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When the number of the energy ray-curable compounds (a 12) constituting the acrylic resin (a 1-1) is 2 or more, the combination and ratio thereof can be arbitrarily selected.
In the acrylic resin (a 1-1), the proportion of the content of the energy ray-curable group derived from the energy ray-curable compound (a 12) relative to the content of the functional group derived from the acrylic polymer (a 11) is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and still more preferably 50 to 100 mol%. When the content ratio is within such a range, the adhesive strength of the cured protective film (X) becomes higher. In the case where the energy ray-curable compound (a 12) is a monofunctional compound (having 1 group in the molecule), the upper limit of the proportion of the above content is 100 mol%, and in the case where the energy ray-curable compound (a 12) is a polyfunctional compound (having 2 or more groups in the molecule of 1), the upper limit of the proportion of the above content exceeds 100 mol%.
The weight average molecular weight (Mw) of the polymer (a 1) is preferably 100000 to 2,000000, more preferably 300000 to 1,500000.
When the polymer (a 1) is a polymer at least a part of which is crosslinked by a crosslinking agent, the polymer (a 1) may be a polymer obtained by polymerizing a monomer having a group which reacts with the crosslinking agent and is not included in any of the monomers described above, which are monomers constituting the acrylic polymer (a 11), and crosslinking the monomer in a group which reacts with the crosslinking agent, or the polymer (a 1) may be a polymer obtained by crosslinking a group which reacts with the functional group and is derived from the energy ray-curable compound (a 12).
The polymer (a 1) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When the number of the polymers (a 1) is 2 or more, the combination and ratio thereof can be arbitrarily selected.
(Compound (a 2))
Examples of the energy ray-curable group of the compound (a 2) having an energy ray-curable group and a weight average molecular weight of 100 to 80000 include a group containing an energy ray-curable double bond, and preferable groups include: (meth) acryloyl group, vinyl group, or the like.
The compound (a 2) is not particularly limited as long as it satisfies the above conditions, and includes: low molecular weight compounds having an energy ray-curable group, epoxy resins having an energy ray-curable group, and phenol resins having an energy ray-curable group, and the like.
Among the compounds (a 2), 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. As the acrylate-based compound, for example: <xnotran> 2- -3- () , () , A () ,2,2- [4- (() ) ] , A () ,2,2- [4- (() ) ] ,9,9- [4- (2- () ) ] ,2,2- [4- (() ) ] , () ,1,10- () ,1,6- () ,1,9- () , () , () , () , () , () , () , () ,2,2- [4- (() ) ] , () , </xnotran> 2-functional (meth) acrylates such as ethoxylated polypropylene glycol di (meth) acrylate and 2-hydroxy-1, 3-di (meth) acryloyloxypropane; 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 or the phenol resin having an energy ray-curable group in the compound (a 2), for example, a resin described in paragraph 0043 of "jp 2013-194102 a" or the like can be used.
The weight average molecular weight of the compound (a 2) is preferably 100 to 30000, more preferably 300 to 10000.
The compound (a 2) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When the number of the compounds (a 2) is 2 or more, the combination and ratio thereof can be arbitrarily selected.
(Polymer (b) having no energy ray-curable group)
When the energy ray-curable resin composition (x 2-1) and the energy ray-curable resin film (x 2) contain the compound (a 2) 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) having no energy ray-curable group may be a polymer at least a part of which is crosslinked by a crosslinking agent, or may be an uncrosslinked polymer.
Examples of the polymer (b) having no energy ray-curable group include: acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, and acrylic urethane resins. Among them, the polymer (b) is preferably an acrylic polymer (hereinafter, may be simply referred to as "acrylic polymer (b-1)").
The acrylic polymer (b-1) may be a known polymer, and may be, for example, a homopolymer of 1 acrylic monomer or a copolymer of 2 or more acrylic monomers. The acrylic polymer (b-1) may be a copolymer of 1 or 2 or more acrylic monomers and 1 or 2 or more monomers (non-acrylic monomers) other than the acrylic monomers.
Examples of the acrylic monomer constituting the acrylic polymer (b-1) include: alkyl (meth) acrylates, (meth) acrylates having a cyclic skeleton, (meth) acrylates containing a glycidyl group, (meth) acrylates containing a hydroxyl group, and (meth) acrylates containing a substituted amino group.
Examples of the alkyl (meth) acrylate include: alkyl (meth) acrylates having a chain structure in which an alkyl group constituting an alkyl ester is a carbon number of 1 to 18, such as 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), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearyl (meth) acrylate).
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 cycloalkoxyalkyl (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, and 4-hydroxybutyl (meth) acrylate.
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 polymers obtained by reacting a 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 is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxyl group, an amino group, and the like, and among them, 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 them, a carboxyl group having high reactivity with an epoxy group is preferable.
Among them, the reactive functional group is preferably a group other than a carboxyl group from the viewpoint of preventing circuit corrosion of a semiconductor wafer or a semiconductor chip.
Examples of the polymer (b) having a reactive functional group and not having an energy ray-curable group include polymers obtained by polymerizing at least a monomer having a reactive functional group. In the case of the acrylic polymer (b-1), any one or both of the acrylic monomer and the non-acrylic monomer listed as the monomer constituting the acrylic polymer may be used as long as the monomer having a reactive functional group is used. 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-mentioned acrylic monomer or non-acrylic monomer, a polymer obtained by polymerizing a monomer in which 1 or 2 or more hydrogen atoms 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 is preferably 1 to 20% by mass, more preferably 2 to 10% by mass, relative to the total mass of the structural units constituting the polymer (b). When the above ratio is in such a range, the degree of crosslinking in the polymer (b) is more preferably in the range.
The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10000 to 2000000, more preferably 100000 to 1500000, from the viewpoint of improving the film-forming property of the energy ray-curable resin composition (x 2-1).
The polymer (b) having no energy ray-curable group may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When the number of the polymers (b) having no energy ray-curable group is 2 or more, the combination and ratio thereof can be arbitrarily selected.
Examples of the energy ray-curable resin composition (x 2-1) include compositions containing either or both of the polymer (a 1) and the compound (a 2).
Among these, when the energy ray-curable resin composition (x 2-1) contains the compound (a 2), it preferably further contains a polymer (b) having no energy ray-curable group, and in this case, it preferably further contains the polymer (a 1).
The energy ray-curable resin composition (x 2-1) may contain the polymer (a 1) and the polymer (b) having no energy ray-curable group, in addition to the compound (a 2).
When the energy ray-curable resin composition (x 2-1) contains the polymer (a 1), the compound (a 2), and the polymer (b) having no energy ray-curable group, the content of the compound (a 2) is preferably 10 to 400 parts by mass, and more preferably 30 to 350 parts by mass, based on 100 parts by mass of the total content of the polymer (a 1) and the polymer (b) having no energy ray-curable group.
The total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass, based on the total amount of the active ingredients of the energy ray-curable resin composition (x 2-1). When the content of the energy ray-curable component is in such a range, the energy ray-curability of the energy ray-curable resin film (x 2) is further improved.
The energy ray-curable resin composition (x 2-1) may contain 1 or 2 or more selected from a thermosetting component, a photopolymerization initiator, a filler, a coupling agent, a crosslinking agent, and a general-purpose additive, in addition to the energy ray-curable component, depending on the purpose.
For example, by using the energy ray-curable resin composition (X2-1) containing the energy ray-curable component and the thermosetting component, the adhesion of the formed energy ray-curable resin film (X2) to an adherend is improved by heating, and the strength of the protective film (X) formed from the energy ray-curable resin film (X2) is also improved.
Examples of the thermosetting component, photopolymerization initiator, filler, coupling agent, crosslinking agent and general-purpose additive in the energy ray-curable resin composition (x 2-1) include the same ones as those of the thermosetting component (B), photopolymerization initiator (H), filler (D), coupling agent (E), crosslinking agent (F) and general-purpose additive (I) in the energy ray-curable resin composition (x 2-1).
In the energy ray-curable resin composition (x 2-1), 1 kind of the thermosetting component, the photopolymerization initiator, the filler, the coupling agent, the crosslinking agent, and the general-purpose additive may be used alone, or 2 or more kinds may be used in combination. When 2 or more kinds are used in combination, the combination and ratio thereof can be arbitrarily selected.
The content of the thermosetting component, photopolymerization initiator, filler, coupling agent, crosslinking agent, and general-purpose additive in the energy ray-curable resin composition (x 2-1) may be appropriately adjusted according to the purpose, and is not particularly limited.
The energy ray-curable resin composition (x 2-1) is preferably further containing a solvent because the workability is improved by dilution.
Examples of the solvent contained in the energy ray-curable resin composition (x 2-1) include the same solvents as those in the thermosetting resin composition (x 1-1).
The solvent contained in the energy ray-curable resin composition (x 2-1) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When 2 or more kinds are used in combination, the combination and ratio thereof can be arbitrarily selected.
(other Components)
The energy ray-curable resin composition (x 2-1) may contain, in addition to the energy ray-curable components, components other than the curable components, i.e., a curing accelerator (C), a filler (D), a coupling agent (E), and the like in an appropriate amount, as in the case of the thermosetting resin film (x 1) described above.
(method for producing energy ray-curable resin composition (x 2-1))
The energy ray-curable resin composition (x 2-1) can be obtained by blending the respective components for constituting the composition. The order of addition of the components in the mixing is not particularly limited, and 2 or more components may be added simultaneously.
When a solvent is used, the solvent may be used by mixing the solvent with any compounding ingredient other than the solvent and diluting the compounding ingredient in advance, or the solvent may be used by mixing the solvent with any compounding ingredient other than the solvent without diluting the compounding ingredient in advance. The method of 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, and the temperature is preferably 15 to 30 ℃.
Supporting plate (Y)
The support sheet (Y) functions as a support for supporting the curable resin film (x).
As shown in fig. 2, the support sheet (Y) may be composed of only the base material 11, may be a laminate of the base material 11 and the adhesive layer 21 as shown in fig. 3, and may be a laminate of the base material 11, the intermediate layer 31, and the adhesive layer 21 stacked in this order as shown in fig. 4. A laminate in which the substrate 11, the intermediate layer 31, and the pressure-sensitive adhesive layer 21 are laminated in this order is suitably used as a back-grinding tape.
The substrate of the support sheet (Y), the pressure-sensitive adhesive layer optionally included in the support sheet (Y), and the intermediate layer will be described below.
< substrate >
The substrate is in the form of a sheet or a film, and the following various resins can be used as the constituent material.
Examples of the resin constituting the substrate 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 2 or more of the above polyesters; poly (meth) acrylates; a polyurethane; a urethane acrylate; a polyimide; a polyamide; a polycarbonate; a fluororesin; a polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfones; polyether ketones, and the like.
Examples of the resin constituting the base material include polymer alloys such as a mixture of the polyester and other resins. The polymer alloy of the polyester and the resin other than polyester is preferably in a small amount.
Examples of the resin constituting the base material include: crosslinked resins obtained by crosslinking 1 or 2 or more of the above resins exemplified so far; modified resins such as ionomers of 1 or 2 or more of the above resins exemplified so far are used.
The resin constituting the base material may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When the number of the resins constituting the base material is 2 or more, the combination and ratio thereof can be arbitrarily selected.
The substrate may be 1 layer (single layer) or a multilayer having 2 or more layers. When the substrate is a multilayer, the layers may be the same as or different from each other, and the combination of the layers is not particularly limited.
The thickness of the substrate is preferably 5 to 1000. Mu.m, more preferably 10 to 500. Mu.m, still more preferably 15 to 300. Mu.m, and still 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 including a plurality of layers refers to the total thickness of all layers constituting the substrate.
The substrate is preferably a substrate having high precision of thickness, that is, a substrate in which variations in thickness are suppressed regardless of the location. Among the above-mentioned constituent materials, examples of such a highly accurate thickness material that can be used to constitute the base material include: polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymers, and the like.
The base material may contain various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer), in addition to the main constituent materials such as the above-mentioned resins.
The substrate may be transparent or opaque, may be colored according to the purpose, or may be vapor-deposited with another layer. In the case where the curable resin film (x) is an energy ray-curable resin film (x 2) or the case where the adhesive layer is an energy ray-curable adhesive layer, the substrate is preferably a substrate that transmits energy rays.
The substrate can be produced 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 them, 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 resin having adhesive properties of the resin itself 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 such as heat or water, and the like.
The pressure-sensitive adhesive layer may be 1 layer (single layer) or 2 or more layers. When the adhesive layer is a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of these plurality of layers is not particularly limited.
The thickness of the 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 including a plurality of layers refers to the total thickness of all layers constituting the pressure-sensitive adhesive layer.
The adhesive layer may be formed using an energy ray-curable adhesive or a non-energy ray-curable adhesive. The adhesive layer formed using the energy ray-curable adhesive can be easily adjusted in physical properties before and after curing.
< intermediate layer >
The intermediate layer is in the form of a sheet or a film, and the material of the intermediate layer may be appropriately selected depending on the purpose, and is not particularly limited. For example, in the case where the shape of the bump existing on the semiconductor surface is reflected on the protective film covering the semiconductor surface, and the deformation of the protective film (X) is suppressed, a preferred constituent material of the intermediate layer is urethane (meth) acrylate from the viewpoint of improving the concave-convex follow-up property, improving the bump penetration property, and further improving the adhesiveness of the intermediate layer.
The intermediate layer may be only 1 layer (single layer) or may be a multilayer having 2 or more layers. When the intermediate layer is a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of these plurality of layers is not particularly limited.
The thickness of the intermediate layer can be appropriately adjusted depending on the height of the bump on the semiconductor surface to be protected, and is preferably 50 to 600 μm, more preferably 70 to 500 μm, and even more preferably 80 to 400 μm, from the viewpoint that the influence of a bump having a high height can be easily absorbed. 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 including a plurality of layers refers to the total thickness of all layers constituting the intermediate layer.
Next, a method for manufacturing the protective film forming sheet will be described.
[ method for producing protective film-forming sheet ]
The protective film-forming sheet can be produced by sequentially laminating the above layers so that the layers are in 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 a support sheet, the adhesive layer or the intermediate layer can 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 curable resin film (x) is further laminated on the adhesive layer already laminated on the substrate, the curable resin film (x) may be directly formed by applying the thermosetting resin composition (x 1-1) or the energy ray-curable resin composition (x 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 2-layer continuous laminate structure is formed using an arbitrary composition, a new layer can be formed by further applying the composition to a layer formed of the composition. Among these 2 layers, the layer to be laminated later is preferably formed in advance on another release film using the above composition, and the exposed surface of the completely formed layer on the side opposite to the side in contact with the release film is preferably bonded to the exposed surfaces of the remaining layers that have been completely formed, thereby preferably forming a laminated structure of 2 continuous layers. In this case, the composition is preferably applied to the release-treated surface of the release film. After the laminated structure is formed, the release film may be removed as needed.
[ method for producing semiconductor wafer with protective film using protective film-forming sheet ]
The method for manufacturing a semiconductor wafer with a protective film according to the present invention can be carried out using the protective film-forming sheet according to the present invention.
Specifically, the method comprises the following steps (S1) to (S3).
Step (S1): process for preparing semiconductor wafer having bump formation surface provided with a plurality of bumps
Step (S2): a step of bonding the protective film-forming sheet of the present invention to the bump-forming surface of the semiconductor wafer while pressing the protective film-forming sheet with a curable resin film (x) as a bonding surface
Step (S3): curing the curable resin film (X) to form a protective film (X)
Hereinafter, a semiconductor wafer to be applied will be described in detail, and a method for manufacturing a semiconductor wafer with a protective film according to the present invention will be described.
< Process (S1) >
In step (S1), a semiconductor wafer having a bump formation surface on which a plurality of bumps are provided is prepared.
Fig. 5 shows an example of a semiconductor wafer having a bump forming surface on which a plurality of bumps are provided, which is used in the method for manufacturing a semiconductor wafer with a protective film according to the present invention. The semiconductor wafer 40 having bumps includes a plurality of bumps BM on a bump formation surface (circuit surface) 41a of a semiconductor wafer 41.
In the following description, the "semiconductor wafer having bumps" is also referred to as a "bumped wafer". The "semiconductor wafer" is also referred to simply as "wafer".
The wafer 41 has circuits such as wiring, a capacitor, a diode, and a transistor formed on a surface thereof. The material of the wafer is not particularly limited, and examples thereof include: silicon wafers, silicon carbide wafers, compound semiconductor wafers, sapphire wafers, glass wafers, and the like.
The size of the wafer 41 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 circle, and may be a quadrangle such as a square or a rectangle. In the case of a square wafer, the length of the longest side of the size of the wafer 41 is preferably equal to or greater than the above size (diameter) from the viewpoint of improving the batch processing efficiency.
The thickness of the wafer 41 is not particularly limited, but is preferably 100 to 1000 μm, more preferably 200 to 900 μm, and still more preferably 300 to 800 μm, from the viewpoint of easily suppressing warpage of the wafer 41 caused by curing the curable resin film (x).
The shape of the bump BM 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. 5, the bump BM is formed in a spherical shape, but the bump BM may be a spheroid. The spheroid may be, for example, a spheroid extending in the vertical direction with respect to the bump forming surface 41a of the wafer 41, or may be a spheroid extending in the horizontal direction with respect to the bump forming surface 41a of the wafer 41.
As shown in fig. 6, the bump BM may have a pillar (pillar) shape.
The material of the bump BM may be, for example, solder.
Here, in the present invention, a semiconductor wafer having bumps with a narrowed pitch defined by the requirements described below is an object of application.
That is, in the present invention, the protective film (X) is formed on the bump formation surface of the semiconductor wafer having the bumps with the narrowed pitch by using the protective film forming sheet, so that the bumps with the narrowed pitch are suppressed from being crushed and deformed, and the short circuit between the bumps is prevented. In other words, the semiconductor wafer to which the present invention is applied is a semiconductor wafer having bumps with narrowed pitches, which may cause a short circuit due to collapse or deformation of the bumps without forming the protective film (X).
The semiconductor wafer described below is a semiconductor wafer having bumps with a narrowed pitch, which may cause a short circuit due to the collapse or deformation of the bumps when the protective film (X) is not formed.
Semiconductor wafer
The protective film forming sheet of the present invention is used for forming a protective film (X) on a bump forming surface of a semiconductor wafer satisfying the following requirements (alpha 1) to (alpha 2).
The method for manufacturing a semiconductor wafer with a protective film according to the present invention is performed using a semiconductor wafer satisfying the following requirements (α 1) to (α 2).
Requirement (α 1): width of the Bump (BM) w ) The unit is 20 to 350 μm.
Requirement (α 2): the pitch (BM) of the above bumps P ) (unit: μm) and the width of the Bump (BM) w ) (unit: μm) satisfies the following formula (I).
[(BM P )/(BM w )]≤1.0····(I)
The above requirements (α 1) to (α 2) are indexes of the semiconductor wafer having the bump with the narrowed pitch. That is, the index indicates that a short circuit due to flattening or deformation of the bump is likely to occur.
To show the pitch (BM) of the bumps P ) (unit: μm) and width of Bump (BM) w ) FIG. 7 is an enlarged plan view of 3 bumps BM _ a, BM _ b and BM _ c formed on the bump formation surface of the wafer 41, which is defined by (unit: μm).
Spacing of Bumps (BM) P ) Is the shortest distance between 2 bumps. In fig. 7, the shortest distance between the bump BM _ a and the bump BM _ b is P 1 . In addition, the shortest distance between the bump BM _ b and the bump BM _ c is P 2 。
Width of Bump (BM) w ) Is connected to b 1 And point b 2 Straight line b of 1 -b 2 Length of (b) 1 Is a straight line P connecting the bump BM _ a and the bump BM _ b 1 Intersection point with the bump BM _ b, b 2 Is a straight line P connecting the bump BM _ b and the bump BM _ c 2 The intersection point with the bump BM _ b.
Note that the pitch of the Bump (BM) P ) (unit: μm) and the width of the Bump (BM) w ) The (unit: μm) can be determined by, for example, optical microscope observation based on the above definition.
When the above requirements (α 1) to (α 2) are satisfied between at least any 1 of a plurality of bumps present on a wafer, the bumps have a narrow pitch, and therefore, there is a risk of short-circuiting between the bumps.
Therefore, the wafer to which the present invention is applied is a wafer in which the above requirements (α 1) to (α 2) are satisfied between at least any 1 of a plurality of bumps present on the wafer.
Here, the width (BM) of the bump defined by the key (alpha 1) w ) The unit is 20 to 350 μm. That is, according to the present invention, the bump width (BM) can be provided w ) A wafer having a plurality of bumps with a size of 20 μm or more and less than 150 μm (particularly, 20 μm to 100 μm) is an object. In other words, a wafer having a plurality of fine bumps with a narrow pitch can be used. In addition, the bump width (BM) can be set w ) A wafer having a plurality of bumps with a size of 150 to 350 μm is used. In other words, a wafer having a plurality of wide bumps with a narrow pitch can be used. A wafer having a narrow pitch and a plurality of wide bumps is particularly likely to cause short-circuiting between bumps, but according to the present invention, such short-circuiting between bumps in the wafer can be suppressed.
Here, the value of [ (BMP)/(BMw) ] defined by the requirement (α 2) is one of the indices indicating the ease with which the bumps are short-circuited, and may be 0.9 or less, or 0.8 or less.
Here, the wafer may satisfy the following requirement (α 3 a) or the following requirement (α 3 b).
Requirement (α 3 a): height of the above Bump (BM) h ) And the width (BM) of the bump w ) Satisfying the following formula (IIIa)
0.2≤[(BM h )/(BM w )]≤1.0····(IIIa)
Requirement (α 3 b): height of the above Bump (BM) h ) And the width (BM) of the bump w ) Satisfying the following formula (IIIb)
0.5≤[(BM h )/(BM w )]≤5.0····(IIIb)
The above requirement (α 3 a) is an index indicating that the bump is a ball bump, [ (BM) h )/(BM w )]The closer to the value of 1.0,the more spherical shape, the more 0.2, the more the ellipsoid of revolution extending in the horizontal direction with respect to the bump forming surface 41a of the wafer 41.
In a semiconductor wafer having such ball bumps, in a step of singulating the semiconductor wafer into semiconductor chips and electrically connecting the semiconductor chips and a wiring substrate via the ball bumps, the ball bumps are flattened and spread in a lateral direction, and the ball bumps come into contact with each other to cause a short circuit. In order to meet the demand for higher density mounting, three-dimensional high density mounting in which semiconductor packages are stacked in the height direction has also been studied, and in this case, the ball bumps are gradually crushed by the weight of the semiconductor package itself, and short-circuiting may be caused. According to the present invention, short-circuiting due to contact between ball bumps can be suppressed.
The above requirement (α 3 b) is an index indicating that the bump is a pillar bump, [ (BM) h )/(BM w )]The closer to 5.0, the more indicative of a high aspect ratio pillar bump, and the closer to 0.5, the more indicative of a low aspect ratio pillar bump.
In a semiconductor wafer having such stud bumps, in a step of singulating the semiconductor wafer into semiconductor chips and electrically connecting the semiconductor chips and a wiring board via the stud bumps, the stud bumps are deformed and bent, and the stud bumps come into contact with each other to cause a short circuit. Further, there is a problem that the connection failure occurs due to deformation and bending of the pillar bump. In order to meet the demand for further high-density mounting, three-dimensional high-density mounting in which semiconductor packages are stacked in the height direction has also been studied, and in this case, the stud bump is gradually crushed by the self weight of the semiconductor package, and therefore, a short circuit may be caused. According to the present invention, short-circuiting due to contact between pillar bumps can be suppressed. In addition, connection failure due to deformation of the pillar bump can also be suppressed.
Note that the height of the Bump (BM) h ) When focusing on 1 bump, the straight line connecting the contact point of the bump with the bump formation surface and the portion of the bump located farthest from the bump formation surfaceThe distance of the line.
Height of Bump (BM) h ) Specifically, the value may be defined by the following requirement (α 4).
Requirement (α 4): height of the Bump (BM) h ) 15 to 300 mu m
That is, in one embodiment of the present invention, the bump height (BM) may be provided h ) A wafer having a plurality of bumps of 20 μm or more and less than 150 μm (particularly, 20 μm to 100 μm) is an object. In addition, the bump height (BM) can be provided h ) A wafer having a plurality of bumps of 150 to 350 μm in height is used.
Height of Bump (BM) h ) The measurement can be performed, for example, by cutting the bumped semiconductor wafer in a direction perpendicular to the bump formation surface and passing through the center of the bump, and observing the cut cross section with an optical microscope.
< Process (S2) >
Fig. 8 shows an outline of the step (S2).
In the step (S2), the protective film forming sheet 1 of the present invention is bonded to the bump forming surface 41a of the semiconductor wafer 41 while being pressed with the curable resin film (x) as the bonding surface.
Thus, the bump forming surface 41a of the semiconductor wafer 41 is covered with the curable resin film (x), and the curable resin film (x) is also filled between the plurality of bumps BM.
The pressing force when the protective film forming sheet 1 is bonded to the bump formation surface 41a of the semiconductor wafer 41 is preferably 1kPa to 200kPa, more preferably 5kPa to 150kPa, and still more preferably 10kPa to 100kPa, from the viewpoint of filling the curable resin film (x) between the plurality of bumps BM well.
The pressing force for bonding the protective film forming sheet 1 to the bump forming surface 41a of the semiconductor wafer 41 may be varied as appropriate from the initial stage to the final stage of the bonding. For example, from the viewpoint of filling the curable resin film (x) more favorably between the plurality of bumps BM, it is preferable to reduce the pressing force at the initial stage of bonding and gradually increase the pressing force.
When the curable resin film (x) is a thermosetting resin film (x 1) in bonding the protective film forming sheet 1 to the bump forming surface 41a of the semiconductor wafer 41, it is preferable to heat the curable resin film (x) from the viewpoint of filling the curable resin film (x) between the plurality of bumps BM more favorably. When the curable resin film (x) is a thermosetting resin film (x 1), the thermosetting resin film (x 1) is heated to temporarily improve the flowability, and is cured by continuing heating. Therefore, by heating the thermosetting resin film (x 1) within a range in which the fluidity of the thermosetting resin film (x 1) is improved, the thermosetting resin film (x 1) is easily filled between the plurality of bumps BM, and the filling property of the thermosetting resin film (x 1) between the plurality of bumps BM is further improved.
The specific heating temperature (bonding temperature) is preferably 50 to 150 ℃, more preferably 60 to 130 ℃, and still more preferably 70 to 110 ℃.
The heat treatment performed on the thermosetting resin film (x 1) is not included in the curing treatment of the thermosetting resin film (x 1).
The protective film forming sheet 1 may be bonded to the bump forming surface 41a of the semiconductor wafer 41 under a reduced pressure atmosphere. This allows negative pressure to be generated between the plurality of bumps BM, and the curable resin film (x) can easily fill the space between the plurality of bumps BM. As a result, the filling property of the curable resin film (x) into the space between the plurality of bumps BM is easily further improved. 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 1kPa.
< Process (S3) >
After the step (S2) is performed, a step (S3) is performed. Specifically, as shown in fig. 9, the curable resin film (x) is cured to obtain a semiconductor wafer with a protective film.
The protective film (X) formed by curing the curable resin film (X) is stronger at room temperature (23 ℃) than the curable resin film (X). Therefore, the bump neck portion can be well protected by forming the protective film (X).
In the present invention, since the protective film forming sheet satisfying the requirements (β 1) to (β 3) is used, as described above, with respect to the semiconductor wafer having the bumps with a narrowed pitch, which has a risk of causing a short circuit due to the collapse and deformation of the bumps, the collapse and deformation of the bumps can be suppressed, and the short circuit due to the contact between the bumps can be avoided.
The curable resin film (x) may be cured by either thermal curing or curing by energy ray irradiation depending on the type of curable component contained in the curable resin film (x).
The conditions for the thermal curing are preferably 90 to 200 ℃ and 1 to 3 hours.
The conditions for curing by irradiation with energy rays may be appropriately set depending on the type of energy rays to be used, and for example, in the case of using ultraviolet rays, the illuminance is preferably 170mw/cm 2 ～250mw/cm 2 The light amount is preferably 300mJ/cm 2 ～3000mJ/cm 2 。
Here, in the process of forming the protective film (X) by curing the curable resin film (X), the curable resin film (X) is preferably a thermosetting resin film (X1) from the viewpoint of removing bubbles and the like sandwiched when filling the plurality of bumps BM with the curable resin film (X) in the step (S2). That is, when the curable resin film (x) is the thermosetting resin film (x 1), the thermosetting resin film (x 1) is heated to temporarily improve the flowability, and is cured by continuous heating. When the fluidity of the thermosetting resin film (x 1) is improved by utilizing this phenomenon, bubbles and the like which are caught when filling the plurality of bumps BM with the thermosetting resin film (x 1) can be removed, and the thermosetting resin film (x 1) can be cured after the filling property of the thermosetting resin film (x 1) into the plurality of bumps BM is further improved.
In addition, the curable resin film (x) is preferably an energy ray curable resin film (x 1) from the viewpoint of shortening the curing time.
The support sheet (Y) is peeled off before the curable resin film (X) is cured, and the curable resin film (X) is cured to form the protective film (X), whereby a semiconductor wafer with a protective film can be obtained. However, the present invention is not limited to such an embodiment, and a semiconductor wafer with a protective film can be obtained by forming the protective film (X) by curing the curable resin film (X) and then peeling off the support sheet (Y).
Further, the semiconductor wafer 41 may be thinned by grinding (back grinding) the surface of the semiconductor wafer 41 opposite to the bump formation surface 41a (i.e., the back surface of the semiconductor wafer 41) without peeling the support sheet (Y). The back grinding treatment may be performed before or after curing the curable resin film (x).
In addition, in the case of performing the back grinding treatment, the supporting sheet (Y) is preferably a back grinding tape from the viewpoint of performing the back grinding treatment well.
After the curable resin film (X) is cured, the protective film (X) covering the top of the bump or the protective film (X) attached to a part of the top of the bump may be removed to expose the top of the bump.
Examples of the exposure process for exposing the top of the bump include an etching process such as a wet etching process and a dry etching process.
Here, the dry etching treatment may be, for example, a plasma etching treatment.
In the case where the top of the bump is not exposed on the surface of the protective film, the exposure treatment may be performed for the purpose of retracting the protective film until the top of the bump is exposed.
[ method for producing semiconductor chip with protective film ]
The method for manufacturing a semiconductor chip with a protective film of the present invention includes the following steps (T1) to (T2).
Step (T1): obtaining a semiconductor wafer with a protective film by carrying out the method for producing a semiconductor wafer with a protective film according to the present invention
Step (T2): a step of singulating the semiconductor wafer with the protective film
< Process (T1) >
In the step (T1), the method for manufacturing a semiconductor wafer with a protective film of the present invention is performed to obtain a semiconductor wafer with a protective film.
< Process (T2) >
In the step (T2), the semiconductor wafer with the protective film obtained in the step (T1) is singulated.
The method of singulation is not particularly limited, and a known singulation method can be appropriately used. Specifically, examples thereof include: laser cutting, blade cutting, stealth cutting (registered trademark), and the like.
Before performing the step (T1), a step of forming a back surface protective film on the back surface (the surface opposite to the bump formation surface) of the semiconductor wafer with the protective film may be included.
[ method for manufacturing semiconductor Package ]
The method for manufacturing a semiconductor package according to the present invention includes the following steps (U1) to (U2).
Step (U1): a step of obtaining a semiconductor chip with a protective film by carrying out the method for manufacturing a semiconductor chip with a protective film of the present invention
Step (U2): a step of electrically connecting the wiring substrate and the semiconductor chip with the protective film via the bump
< Process (U1) >
In the step (U1), the method for manufacturing a semiconductor chip with a protective film according to the present invention is performed to obtain a semiconductor chip with a protective film.
< Process (U2) >
As shown in fig. 10, in the step (U2), the wiring substrate (Z) having the wiring Z1 and the semiconductor chip CP with the protective film are electrically connected via the bump BM.
More specifically, the bump formation surface of the semiconductor chip CP with the protective film is heated in a state where the bump formation surface faces the formation surface of the wiring Z1 of the wiring substrate (Z) with the bump BM interposed therebetween (hereinafter, also referred to as a "heating connection step"). This allows the top of the bump BM to be electrically connected to the wiring Z1 satisfactorily.
In addition, in the present invention, although the semiconductor chip obtained from the semiconductor wafer having the bumps with a narrowed pitch, which may cause a short circuit due to the collapse and deformation of the bumps, is used, the protective film forming sheet of the present invention satisfies the above requirements (β 1) to (β 3), and particularly satisfies the above requirement (β 2), so that the bumps can be prevented from coming into contact with each other due to the collapse and deformation of the bumps in the heat bonding step, and the short circuit due to the contact of the bumps can be avoided.
The conditions of the heating and joining step are, for example, a temperature of 250 to 270 ℃ and a time of 30 seconds to 5 minutes.
< Process (U3) >
The method for manufacturing a semiconductor package according to an embodiment of the present invention further includes the following step (U3).
Step (U3): a step of filling an underfill material between the wiring substrate and the semiconductor chip with the protective film
In the present invention, as described above, the bumps can be prevented from contacting each other due to the squashing and deformation of the bumps. In other words, the bumps can be prevented from approaching each other due to the crush and deformation of the bumps. Conventionally, if bumps are close to each other, even if it is intended to fill the underfill material, the gap between the bumps is narrow, and it is difficult to fill the gap with the underfill material. However, in the present invention, since the approach of the bumps is suppressed, the gap between the protective film (X) and the wiring substrate (Z), including the gap between the bumps, can be satisfactorily filled with the underfill material.
Examples
The present invention will be specifically described with reference to the following examples, but the present invention is not limited to the following examples.
[ methods of measuring various physical Property values ]
The physical property values in the following examples and comparative examples are values measured by the following methods.
< weight average molecular weight >
The measurement was performed under the following conditions using a gel permeation chromatography apparatus (product name "HLC-8020" manufactured by Tosoh corporation), and the value measured in terms of standard polystyrene was used.
(measurement conditions)
A chromatographic column: a chromatographic column formed by sequentially connecting TSK guard column HXL-L, TSK gel G2500HXL, TSK gel G2000HXL and TSK gel G1000HXL (all manufactured by Tosoh Corp.)
Column temperature: 40 deg.C
Elution solvent: tetrahydrofuran (THF)
Flow rate: 1.0mL/min
< measurement of thickness of each layer >
The thickness of the protective film (after curing) other than the thickness (XT) was measured using a constant pressure thickness measuring instrument (model: PG-02J, standard Specification: in accordance with JIS K6783, Z1702, Z1709) manufactured by Telock.
< glass transition temperature >
The glass transition temperature (Tg) of the polymer component (A) described later was determined by measuring a temperature curve from-70 ℃ to 150 ℃ at an increasing/decreasing rate of 10 ℃ per minute using a differential scanning calorimeter (PYRIS Diamond DSC) manufactured by Perkinelmer, and confirming the inflection point.
< epoxy equivalent >
Measured according to JIS K7236.
< average particle diameter >
The particles to be measured were dispersed in water by ultrasonic waves, and the particle size distribution of the particles was measured on a volume basis by a dynamic light scattering method particle size distribution measuring apparatus (LB-550, manufactured by horiba, ltd.), and the median particle diameter (D) was determined 50 ) As the average particle diameter.
Examples 1 to 4 and comparative examples 1 to 2
Production of thermosetting resin film (x 1) used in examples the thermosetting resin composition (x 1-1) used was prepared by the following method.
< raw Material of thermosetting resin composition (x 1-1) >
(Polymer component (A))
Polyvinyl butyral (S-LEC (registered trademark) B BL-10, manufactured by Water-logging chemical Co., ltd., weight average molecular weight 25000, glass transition temperature 59 ℃ C., wherein p is 68 to 74 mol%, q is 1 to 3 mol%, and r is about 28 mol%) having a structural unit represented by the following formula (i-1), the following formula (i-2), and the following formula (i-3) was used.
[ chemical formula 2]
Figure BDA0003840839940000441
(epoxy resin (B1))
The following 2 epoxy resins were used.
Epoxy resin (B1-1): liquid bisphenol A epoxy resin (EPICLON (registered trademark) EXA-4850-1000, manufactured by DIC corporation, epoxy equivalent 404-412 g/eq)
Epoxy resin (B1-2): dicyclopentadiene type epoxy resin (EPICLON (registered trademark) HP-7200, epoxy equivalent 254-264 g/eq, available from DIC corporation)
(Heat-curing agent (B2))
A novolak-type phenol resin (Showa Denko K.K., shonol (registered trademark) BRG-556) was used.
(curing Accelerator (C))
2-phenyl-4, 5-dimethylolimidazole (product of Kasei K.K., curezol (registered trademark) 2 PHZ) was used.
(Filler (D))
Spherical silica modified with epoxy groups (Admatech corporation, admanano (registered trademark) YA050C-MKK, average particle diameter 0.05. Mu.m) was used.
< preparation of thermosetting resin composition (x 1-1) >
The polymer component (a), the epoxy resin (B1-1), the epoxy resin (B1-2), the thermosetting agent (B2), the curing accelerator (C), and the filler (D) were dissolved or dispersed in methyl ethyl ketone so as to be contained in the following amounts based on the total amount (100 mass%) of the thermosetting resin composition (x 1-1), and stirred at 23 ℃.
In examples 1 and 2, the protective film (X) was formed using the thermosetting resin composition (X1-1) prepared according to formulation 1 shown below. In examples 3 and 4, the protective film (X) was formed using the thermosetting resin composition (X1-1) prepared according to formulation 2 shown below.
(Compulsory 1)
Polymer component (a): 41.4% by mass
Epoxy resin (B1-1): 23.2% by mass
Epoxy resin (B1-2): 15.2% by mass
Thermal curing agent (B2): 11.2% by mass
Curing accelerator (C): 0.2% by mass
Filler (D): 8.8% by mass
(coordination 2)
Polymer component (a): 19.9% by mass
Epoxy resin (B1-1): 33.1% by mass
Epoxy resin (B1-2): 21.7% by mass
Thermal curing agent (B2): 16.1% by mass
Curing accelerator (C): 0.2% by mass
Filler (D): 9.0% by mass
< production of thermosetting resin film (x 1) >
The thermosetting resin composition (x 1-1) prepared in accordance with formulation 1 was applied to a release treated surface of a polyethylene terephthalate release material (SP-PET 381031, manufactured by Lindceko Co., ltd., thickness 38 μm) having a release treated surface subjected to a silicone-based release treatment, and dried by heating at 120 ℃ for 2 minutes to obtain a thermosetting resin film (x 1: formulation 1) having a thickness of 30 μm. A thermosetting resin film (x 1: blend 2) having a thickness of 50 μm was obtained in the same manner as above except that the thermosetting resin composition (x 1-1) prepared according to blend 2 was used instead.
< production of sheet for Forming protective film >
As the supporting sheet (Y), an adhesive tape (E-8510 HR, manufactured by Linekekco) obtained by laminating a base material (thickness: 100 μm), an intermediate layer (thickness: 400 μm) and an adhesive layer (thickness: 10 μm) in this order was used, and the adhesive layer of the adhesive tape was laminated with a thermosetting resin film (x 1: blend 1) having a thickness of 30 μm formed on a release material to produce a protective film-forming sheet 1 in which the supporting sheet (Y), the thermosetting resin film (x 1) and the release material were laminated in this order.
A protective film-forming sheet 2 was also produced by the same procedure for a thermosetting resin film (x 1: blend 2) having a thickness of 50 μm.
[ measurement of tensile modulus E' of protective film (X) ]
After curing the thermosetting resin film (X1), the tensile modulus E' of the protective film (X) was measured by the following method.
First, 6 sheets of a thermosetting resin film (x 1: blend 1) having a thickness of 30 μm were stacked to prepare a sample having a thickness of 0.18mm, a width of 4.5mm and a length of 20.0mm, and the sample was heated in a pressurized oven (RAD-9100, manufactured by Lindceko Co., ltd.) at a temperature of: 130 ℃ and time: 2h, pressure in the furnace: the sample was heat-treated under a heating condition of 0.5MPa to obtain a protective film (X).
Subsequently, the tensile modulus E' (23 ℃) of the protective film (X) was measured in a tensile mode at a frequency of 11Hz and 23 ℃ in an atmospheric atmosphere using a dynamic viscoelasticity measuring apparatus (product name "DMA Q800" manufactured by TA instruments). The tensile modulus E' (260 ℃) of the protective film (X) was measured under the same conditions except that the temperature during measurement was set to 260 ℃.
The protective film (X) was obtained by the same procedure except that 4 thermosetting resin films (X1: blend 2) having a thickness of 50 μm were stacked on top of each other and the thickness was set to 0.20mm, and the tensile modulus E '(23 ℃) and the tensile modulus E' (260 ℃) of the protective film (X) were measured.
[ short-circuit evaluation ]
The release material is removed from the protective film forming sheet obtained as described above, and the surface (exposed surface) of the thermosetting resin layer exposed thereby is pressure-bonded to the bump forming surface of the ball-bumped wafer, whereby the protective film forming sheet is attached to the bump forming surface of the semiconductor wafer. At this time, the sheet for forming the protective film was bonded by using a bonding apparatus (a roll laminator, "RAD-3510F/12" manufactured by Lindera corporation) under conditions of a table temperature of 90 ℃, a bonding speed of 2mm/sec, and a bonding pressure of 0.5MPa while heating the thermosetting resin film (x 1). Details of the bumped wafer to which the protective film forming sheet 1 or 2 was attached (requirements (α 1), (α 2), (α 3 a), and (α 4)) are shown in table 1.
Then, the support sheet (Y) of the protective film-forming sheet was peeled off by ultraviolet irradiation using RAD-2700 manufactured by Linekec corporation.
The bumped wafer having the thermosetting resin film (x 1) attached thereto was put in a pressurized oven (RAD-9100, ltd. Ledeb) at a temperature of: 130 ℃, time: 2h, pressure in the furnace: the thermosetting resin film (X1) was thermally cured under a heating condition of 0.5MPa, and the semiconductor wafer with the protective film (X) was obtained (examples 1 to 4).
The semiconductor wafer with the protective film (X) was cut in a direction perpendicular to the bump formation surface and passing through the bump center, and the thickness (X) of the protective film (X) was measured by observing the cut cross section with an optical microscope T )。
Then, the bump formation surface of the semiconductor wafer with the protective film (X) was subjected to a heat treatment (heat connection step) at 260 ℃ for 1 minute while the bump formation surface of the wiring substrate was opposed to the wiring formation surface of the semiconductor wafer with the bump interposed therebetween, and the presence or absence of contact between the bumps (presence or absence of short-circuiting) was evaluated.
As a comparative test, a heat bonding process was performed on a bumped wafer which was the same as in examples 1 and 3 and examples 2 and 4 and on which the protective film (X) was not formed, and the presence or absence of short circuit was evaluated (comparative examples 1 and 2).
The results are shown in Table 1.
[ Table 1]
Figure BDA0003840839940000471
The following conclusions can be drawn from Table 1.
In examples 1 to 4, although the semiconductor wafer having the bumps with the narrowed pitch was used, the bumps were short-circuited.
On the other hand, it is found that, in the case where the protective film (X) is not provided as in comparative examples 1 and 2, the bump short circuit of the semiconductor wafer having the bump with the narrowed pitch cannot be suppressed.

Claims (9)

1. A protective film-forming sheet having a laminated structure of a curable resin film (x) and a support sheet (Y),
the protective film-forming sheet is used for forming a protective film (X) on a bump-forming surface of a semiconductor wafer having a plurality of bumps and satisfying the following requirements (alpha 1) - (alpha 2),
requirement (α 1): width of the Bump (BM) w ) The unit is 20-350 μm,
requirement (α 2): pitch of said Bumps (BM) P ) (unit: μm) and the width of the Bump (BM) w ) (unit: μm) satisfies the following formula (I),
[(BM P )/(BM w )]≤1.0····(I)
wherein the protective film-forming sheet satisfies the following requirements (β 1) to (β 3),
requirement (β 1): a protective film (X) formed by curing the curable resin film (X) has a tensile modulus E' (23 ℃) of 1X 10 at 23 ℃ 7 Pa～1×10 10 Pa，
Requirement (β 2): a protective film (X) formed by curing the curable resin film (X) has a tensile modulus E' (260 ℃) of 1X 10 at 260 DEG 5 Pa～1×10 8 Pa，
Requirement (β 3): a protective film (X) formed by curing the curable resin film (X) has a thickness (X) at 23 DEG C T ) (unit: μm) and the height of the Bump (BM) h ) (unit: μm) satisfies the following formula (II),
[(X T )/(BM h )]≥0.2····(II)。
2. the protective film-forming sheet according to claim 1, which further satisfies the following requirement (α 3 a),
requirement (α 3 a): height of the Bump (BM) h ) And the width (BM) of the bump w ) Is full ofWhich is represented by the following formula (IIIa),
0.2≤[(BM h )/(BM w )]≤1.0····(IIIa)。
3. the protective film-forming sheet according to claim 1, which further satisfies the following requirement (α 3 b),
requirement (α 3 b): height of the Bump (BM) h ) And the width (BM) of the bump w ) Satisfies the following formula (IIIb),
0.5≤[(BM h )/(BM w )]≤5.0····(IIIb)。
4. the protective film-forming sheet according to any one of claims 1 to 3, which further satisfies the following requirement (α 4),
requirement (α 4): height of the Bump (BM) h ) Is 15-300 μm.
5. The protective film-forming sheet according to any one of claims 1 to 4,
the support sheet (Y) is a back grinding adhesive tape.
6. A method for manufacturing a semiconductor wafer with a protective film, comprising the steps (S1) to (S3),
step (S1): preparing a semiconductor wafer having a bump formation surface provided with a plurality of bumps;
step (S2): a step of bonding the protective film forming sheet according to any one of claims 1 to 5 to the bump forming surface of the semiconductor wafer while pressing the protective film forming sheet with a curable resin film (x) as a bonding surface;
step (S3): a step of curing the curable resin film (X) to form a protective film (X),
wherein the semiconductor wafer prepared in the step (S1) satisfies the following requirements (alpha 1) to (alpha 2),
requirement (α 1): width of the Bump (BM) w ) The unit is 20-350 μm,
requirement (α 2): pitch of said Bumps (BM) P ) (unit: μm) and the width of the Bump (BM) w ) (unit: μm) satisfies the following formula (I),
[(BM P )/(BM w )]≤1.0····(I)。
7. a method for manufacturing a semiconductor chip with a protective film, comprising the steps (T1) to (T2),
step (T1): a step of obtaining a semiconductor wafer with a protective film by carrying out the production method according to claim 6,
step (T2): and a step of dividing the semiconductor wafer with the protective film into individual pieces.
8. A method for manufacturing a semiconductor package, comprising the following steps (U1) to (U2),
step (U1): a step of obtaining a semiconductor chip with a protective film by performing the manufacturing method according to claim 7,
step (U2): and electrically connecting the wiring substrate and the semiconductor chip with the protective film via the bump.
9. The method for manufacturing a semiconductor package according to claim 8, further comprising a step (U3),
step (U3): and filling an underfill material between the wiring substrate and the semiconductor chip with the protective film.
CN202180020576.2A 2020-03-12 2021-03-11 Protective film forming sheet Pending CN115244654A (en)

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