CN116515237A - Curable resin film, composite sheet, semiconductor chip, and method for manufacturing semiconductor chip - Google Patents

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

Info

Publication number
CN116515237A
CN116515237A CN202310085287.1A CN202310085287A CN116515237A CN 116515237 A CN116515237 A CN 116515237A CN 202310085287 A CN202310085287 A CN 202310085287A CN 116515237 A CN116515237 A CN 116515237A
Authority
CN
China
Prior art keywords
resin film
curable resin
semiconductor chip
wafer
bump formation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310085287.1A
Other languages
Chinese (zh)
Inventor
贝沼玲菜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lintec Corp
Original Assignee
Lintec Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lintec Corp filed Critical Lintec Corp
Publication of CN116515237A publication Critical patent/CN116515237A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • H01L23/3185—Partial encapsulation or coating the coating covering also the sidewalls of the semiconductor body
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H01L23/3157—Partial encapsulation or coating
    • H01L23/3171—Partial encapsulation or coating the coating being directly applied to the semiconductor body, e.g. passivation layer
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Abstract

The present invention provides a curable resin film for forming a protective film on both a bump formation surface and a side surface of a semiconductor chip having the bump formation surface, wherein the curable resin film has an elongation at break of 85% or less at 70 ℃ after curing.

Description

Curable resin film, composite sheet, semiconductor chip, and method for manufacturing semiconductor chip
Technical Field
The present invention relates to a curable resin film, a composite sheet, a semiconductor chip, and a method for manufacturing a semiconductor chip. More specifically, the present invention relates to a curable resin film, a composite sheet provided with the curable resin film, a semiconductor chip provided with the curable resin film as a protective film by using the curable resin film and the composite sheet, and a method for manufacturing the semiconductor chip.
Background
In recent years, a semiconductor device has been manufactured using a mounting method called a flip-chip method. In the flip-chip method, a semiconductor chip having bumps on a circuit surface and a substrate for mounting the semiconductor chip are stacked such that the circuit surface of the semiconductor chip faces the substrate, whereby the semiconductor chip is mounted on the substrate.
The semiconductor chip is generally obtained by singulating a semiconductor wafer having bumps on a circuit surface.
For the semiconductor wafer provided with the bumps, a protective film may be provided for the purpose of protecting the joint portions (hereinafter also referred to as "bump necks") of the bumps and the semiconductor wafer.
For example, in patent document 1 and patent document 2, a laminate of a support substrate, an adhesive layer, and a thermosetting resin layer laminated in this order is pressed against and bonded to a bump formation surface of a semiconductor wafer provided with bumps with the thermosetting resin layer as a bonding surface, and then the thermosetting resin layer is heated and cured, whereby a protective film is formed.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2015-092594
Patent document 2: japanese patent application laid-open No. 2012-169484
Disclosure of Invention
Problems to be solved by the invention
In the methods described in patent document 1 and patent document 2, a protective film is formed on a bumped wafer, and then the bumped wafer is diced together with the protective film, whereby singulated semiconductor chips are obtained. In this way, when dicing the bumped wafer together with the protective film, the processing quality of the cut surface of the protective film formed by the dicing blade is good.
However, the present inventors have intensively studied and found that, when a protective film is formed on both the bump formation surface and the side surface of a semiconductor chip having the bump formation surface, there is a problem in that the processing quality of the cut surface of the protective film formed by a dicing blade is lowered.
The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a curable resin film which is useful for forming a protective film on both the bump formation surface and the side surface of a semiconductor chip having a bump formation surface, and which is excellent in processing quality after grinding and singulation, a composite sheet including the curable resin film, a semiconductor chip, and a method for manufacturing the semiconductor chip.
Means for solving the problems
As a result of intensive studies to solve the above-described problems, the present inventors have found that, when a protective film is formed on both the bump formation surface and the side surface of a semiconductor chip having a bump formation surface, the wafer is not cut by a dicing blade, but only the wafer protective film is cut, and therefore the processing quality of the cut surface of the protective film formed by the dicing blade is reduced. The present inventors have made intensive studies with a view to solving the above problems, focusing on the physical properties of a curable resin film used for forming a protective film. As a result, it has been found that the above problems can be solved by using a curable resin film having an elongation at break of a specific value or less at 70 ℃ after curing for the formation of a protective film for a semiconductor chip, and the present invention has been completed.
That is, the present invention relates to the following modes.
[1] A curable resin film for forming a protective film on both a bump formation surface and a side surface of a semiconductor chip having the bump formation surface,
wherein the elongation at break of the curable resin film after curing at 70 ℃ is 85% or less.
[2] The curable resin film according to [1], wherein the product of elongation at break and energy at break at 70 ℃ after curing of the curable resin film is 1000 or less.
[3] The curable resin film according to [1] or [2], which has a thickness of 30 μm or more.
[4] A composite sheet having a laminated structure obtained by laminating the curable resin film according to any one of [1] to [3] above and a release sheet.
[5] The composite sheet according to the above [4], wherein the release sheet has a base material and a release layer, and the release layer faces the curable resin film.
[6] The composite sheet according to the above [5], further comprising an intermediate layer between the base material and the release layer.
[7] The composite sheet according to the above [5] or [6], wherein the release layer is a layer formed of a composition containing an ethylene-vinyl acetate copolymer.
[8] A method for manufacturing a semiconductor chip, comprising the following steps (S1) to (S4) in this order,
step (S1): a step of preparing a wafer for semiconductor chip production having a groove as a dividing line formed in a bump formation surface of a semiconductor wafer having the bump formation surface of a bump so as not to reach a back surface;
step (S2): pressing and adhering the curable resin film of any one of [1] to [3] to the bump formation surface of the semiconductor chip manufacturing wafer, coating the bump formation surface of the semiconductor chip manufacturing wafer with the curable resin film, and embedding the curable resin film in the groove portion of the semiconductor chip manufacturing wafer;
step (S3): a step of curing the curable resin film to obtain a wafer for manufacturing a semiconductor chip having a cured resin film;
step (S4): a step of singulating the wafer for manufacturing semiconductor chips with the cured resin film along the predetermined dividing lines to obtain semiconductor chips having at least the bump formation surfaces and the side surfaces covered with the cured resin film;
And, after the step (S2) and before the step (S3), after the step (S3) and before the step (S4), or in the step (S4), the method comprises the following step (S-BG),
step (S-BG): and grinding the back surface of the wafer for manufacturing the semiconductor chip.
[9] A semiconductor chip having a cured resin film obtained by curing the curable resin film of any one of [1] to [3] on both the bump formation surface and the side surface of the semiconductor chip having the bump formation surface.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a curable resin film that is useful for forming a protective film on both the bump formation surface and the side surface of a semiconductor chip having a bump formation surface, and that is excellent in processing quality after grinding and singulation, a composite sheet including the curable resin film, a semiconductor chip, and a method for manufacturing the semiconductor chip can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view showing the structure of a composite sheet according to an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view showing the constitution of a composite sheet according to another embodiment of the present invention.
Fig. 3 is a schematic cross-sectional view showing an example of the wafer for manufacturing semiconductor chips prepared in the step (S1).
Fig. 4 is a diagram showing an outline of the step (S2).
Fig. 5 is a diagram showing an outline of the step (S3).
Fig. 6 is a diagram showing an outline of the step (S4).
Fig. 7 is a diagram showing an outline of the procedure (S-BG).
Symbol description
10. 20 composite sheet
30. Wafer for manufacturing semiconductor chip
40. Semiconductor chip
1. 11 stripping sheet
2. 12 curable resin film
3. 13 substrate
4. 14 release layer
15. Intermediate layer
21. Semiconductor wafer
21a bump formation face
21b back face
22. Bump block
23. Groove part
X1 first curable resin film
Y1 first release sheet
r1 first cured resin film
Alpha 1 first composite sheet
X2 second curable resin film
Y2 second stripping sheet
r2 second cured resin film
Alpha 2 second composite sheet
Detailed Description
In the present specification, the term "active ingredient" refers to a component other than water and a diluting solvent such as an organic solvent among components included in the composition to be targeted.
In the present specification, "(meth) acrylic acid" means both "acrylic acid" and "methacrylic acid", and other similar expressions are also used.
In the present specification, the weight average molecular weight and the number average molecular weight are polystyrene equivalent values measured by Gel Permeation Chromatography (GPC).
In the present specification, the lower limit value and the upper limit value described in stages may be independently combined with each other in a preferable numerical range (for example, a range of content or the like). For example, according to the description of "preferably 10 to 90, more preferably 30 to 60", the "preferable lower limit value (10)" and the "more preferable upper limit value (60)" may be combined to obtain "10 to 60".
[ curable resin film ]
The curable resin film of the present invention is used for forming a curable resin film as a protective film on both the bump formation surface and the side surface of a semiconductor chip having a bump formation surface, wherein the curable resin film has an elongation at break of 85% or less at 70 ℃ after curing.
When the elongation at break of the curable resin film after curing at 70 ℃ exceeds 85%, deformation and cutting chips due to elongation of the curable resin film caused by frictional heat are likely to occur when the curable resin film is buried in a groove formed in a wafer for semiconductor chip production and the cured resin film formed by curing the curable resin film is cut along a line to cut in the manufacturing process of semiconductor chips. Therefore, there is a risk that deformation of the cut surface of the wafer for manufacturing semiconductor chips occurs and adhesion of the cutting chips to the cut surface, resulting in degradation of the processing quality of the obtained semiconductor chips. From such a viewpoint, the elongation at break is preferably 65% or less, more preferably 45% or less, further preferably 40% or less, further preferably 30% or less, further preferably 20% or less. The lower limit of the elongation at break is not particularly limited, and may be 1% or more, or 3% or more.
The elongation at break can be adjusted by adjusting either or both of the kind and amount of the component contained in the curable resin forming the curable resin film.
The elongation at break can be measured by the method described in examples.
The curable resin film of the present invention preferably has a breaking energy of 10.0MJ/m at 70℃after curing 3 Hereinafter, more preferably 9.0MJ/m 3 The following is more preferably 7.0MJ/m 3 The following is more preferably 6.0MJ/m 3 The following is more preferably 3.0MJ/m 3 The following is given. When the fracture energy is equal to or less than the above value, in the semiconductor chip manufacturing process, the curable resin film is embedded in the groove formed in the semiconductor chip manufacturing wafer, and the cured resin film formed by curing the curable resin film is formed along the grooveWhen the line to be divided is cut, the generated cutting scraps become small, and the cutting scraps are less likely to remain in the groove portion as a retentate. Therefore, the retentate is less likely to adhere to the cut surface of the wafer for manufacturing semiconductor chips, and semiconductor chips with excellent processing quality can be obtained. The lower limit of the breaking energy is not particularly limited, but is preferably 0.1MJ/m 3 The above.
The fracture energy can be adjusted by adjusting either one or both of the kind and amount of the component contained in the curable resin forming the curable resin film.
The fracture energy may be measured by the method described in examples.
The product of the elongation at break (T) and the energy at break (E) at 70 ℃ after curing of the curable resin film of the present invention is preferably 1000 or less, more preferably 850 or less, still more preferably 650 or less, still more preferably 450 or less, still more preferably 300 or less, still more preferably 200 or less. When the product of the elongation at break (T) and the breaking energy (E) is equal to or less than the above value, the cutting chips and the retentate are suppressed in the manufacturing process of the semiconductor chip, and the processing quality of the obtained semiconductor chip can be improved. The lower limit of the product of the elongation at break and the breaking energy is not particularly limited, and may be 1 or more.
The curable resin film of the present invention preferably satisfies the following requirement (I) from the viewpoint of forming a protective film excellent in coating properties with respect to both the bump formation surface and the side surface of the semiconductor chip.
< requirement (I) >)
A test piece of the curable resin film having a diameter of 25mm and a thickness of 1mm is strained at a temperature of 90 ℃ and a frequency of 1Hz, the storage modulus of the test piece is measured, the storage modulus of the test piece when the strain of the test piece is 1% is Gc1, and the storage modulus of the test piece when the strain of the test piece is 300% is Gc300, and at this time, the X value calculated by the following formula (i) is 10 or more and less than 10,000.
X＝Gc1/Gc300····(i)
The upper limit of the X value defined in the above-mentioned element (I) is preferably 5,000 or less, more preferably 2,000 or less, further preferably 1,000 or less, further preferably 500 or less, further preferably 300 or less, more preferably 100 or less, further preferably 70 or less, from the viewpoint of forming a protective film excellent in coating property.
In addition, from the viewpoint of improving the embeddability into the groove of the wafer for producing semiconductor chips, the lower limit of the X value defined in the above-mentioned element (I) is preferably 20 or more, more preferably 30 or more.
In the curable resin film of the present invention, gc1 is not particularly limited as long as the X value defined in the above-mentioned element (I) is 10 or more and less than 10,000.
Among them, gc1 is preferably 1×10 from the viewpoint of easier formation of a protective film excellent in coating property 2 ～1×10 6 Pa, more preferably 2X 10 3 ～7×10 5 Pa, and more preferably 3X 10 3 ～5×10 5 Pa。
In the curable resin film of the present invention, gc300 is not particularly limited as long as X value is 10 or more and less than 10,000.
Among them, gc300 is preferably 10 to 15,000pa, more preferably 30 to 10,000pa, and even more preferably 60 to 5,000pa, from the viewpoint of improving the embeddability of the curable resin film into the bump base portion and the embeddability of the curable resin film into the groove portion of the wafer for semiconductor chip production after the bump penetrates the curable resin film.
The crosslinking density of the curable resin film of the present invention is preferably 0.20 to 0.70mol/ml, more preferably 0.40 to 0.60mol/ml, and even more preferably 0.45 to 0.49mol/ml, from the viewpoint of processing quality of the chip after processing and reduction of the retentate.
The crosslinking density may be calculated by the method described in examples described later.
The thickness of the curable resin film of the present invention is preferably 30 μm or more, more preferably 40 μm or more, and still more preferably 45 μm or more, from the viewpoint of good filling property into the groove. In addition, from the viewpoint of suppressing contamination due to bleeding at the time of adhesion, the thickness of the curable resin film is preferably 250 μm or less, more preferably 200 μm or less, and still more preferably 150 μm or less.
The volume of the resin to be filled varies depending on the depth and width of the groove provided in the wafer for manufacturing a semiconductor chip, and therefore the thickness can be appropriately adjusted.
Here, the "thickness of the curable resin film" refers to the thickness of the entire curable resin film, and for example, the thickness of the curable resin film including a plurality of layers refers to the total thickness of all the layers constituting the curable resin film.
The curable resin film of the present invention is a film for filling a groove formed in a wafer for producing a semiconductor chip while covering a bump formation surface of the wafer for producing a semiconductor chip, and is formed by curing by heating or irradiation of energy rays. The curable resin film may be a thermosetting resin film cured by heating or an energy ray curable resin film cured by irradiation with energy rays, and is preferably a thermosetting resin film from the viewpoint of more easily exhibiting the effect of the present invention.
Hereinafter, the thermosetting resin film will be described.
(thermosetting resin film)
The thermosetting resin film contains a polymer component (A) and a thermosetting component (B). The thermosetting resin film is formed, for example, from a thermosetting resin composition containing a polymer component (a) and a thermosetting component (B).
The polymer component (a) is a component which can be considered to be formed by polymerization of a polymerizable compound. The thermosetting component (B) is a component capable of undergoing a curing (polymerization) reaction by thermally triggering the reaction. The curing (polymerization) reaction also includes a polycondensation reaction.
In the following description of the present specification, "the content of each component based on the total amount of the active components of the thermosetting resin composition" is the same as "the content of each component of the thermosetting resin film formed from the thermosetting resin composition".
[ Polymer component (A) ]
The thermosetting resin film and the thermosetting resin composition contain a polymer component (A).
The polymer component (a) is a polymer compound for imparting film forming property, flexibility, and the like to the thermosetting resin film. The polymer component (A) may be used alone or in combination of 1 or more than 2. In the case where 2 or more polymer components (A) are used in combination, their combination and ratio can be arbitrarily selected.
Examples of the polymer component (a) include: acrylic resin (resin having (meth) acryl), polyarylate resin, polyvinyl acetal, polyester, urethane resin (resin having urethane bond), acrylic urethane resin, silicone resin (resin having siloxane bond), rubber resin (resin having rubber structure), phenoxy resin, thermosetting polyimide, and the like.
Among them, acrylic resins, polyarylate resins and polyvinyl acetals are preferable.
The acrylic resin may be a known acrylic polymer.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 ～ 2,000,000, more preferably 300,000 ～ 1,500,000, and further preferably 500,000 ～ 1,000,000.
When the weight average molecular weight of the acrylic resin is equal to or higher than the lower limit, the shape stability (stability with time during storage) of the thermosetting resin film can be easily improved. In addition, when the weight average molecular weight of the acrylic resin is equal to or less than the upper limit value, the thermosetting resin film is liable to follow the uneven surface of the adherend, and for example, generation of voids or the like between the adherend and the thermosetting resin film is liable to be suppressed. Therefore, the semiconductor wafer has good coating properties on the bump formation surface, and the embedding property into the groove portion is easily improved.
From the viewpoints of adhesion and handleability of the curable resin film, the glass transition temperature (Tg) of the acrylic resin is preferably-60 to 70 ℃, more preferably-40 to 50 ℃, and even more preferably-30 to 30 ℃.
Examples of the acrylic resin include: polymers of 1 or 2 or more (meth) acrylic esters; copolymers of 2 or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, and the like.
Examples of the (meth) acrylate constituting the acrylic resin include: alkyl groups constituting alkyl esters 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, myristyl (meth) acrylate, pentadecyl (meth) acrylate, cetyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, and stearyl (meth) acrylate have a carbon number of 1 to 18 (meth) alkyl groups;
Cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
aralkyl (meth) acrylates such as benzyl (meth) acrylate;
cycloalkenyl (meth) acrylates such as dicyclopentenyl (meth) acrylate;
cycloalkenyloxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate;
(meth) acrylic acid imides;
glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate;
hydroxy-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;
substituted amino group-containing (meth) acrylates such as N-methylaminoethyl (meth) acrylate, and the like.
In the present specification, the term "substituted amino group" refers to a group in which 1 or 2 hydrogen atoms of an amino group are substituted with groups other than hydrogen atoms.
Among them, from the viewpoints of film forming property of the curable resin film and adhesion property of the curable resin film to the protective film forming surface of the semiconductor chip, a copolymer in which an alkyl (meth) acrylate having a chain structure in which an alkyl group constituting the alkyl ester has 1 to 18 carbon atoms, a glycidyl group-containing (meth) acrylate, and a hydroxyl group-containing (meth) acrylate are combined is preferable, and a copolymer in which an alkyl (meth) acrylate having a chain structure in which an alkyl group constituting the alkyl ester has 1 to 4 carbon atoms, a glycidyl group-containing (meth) acrylate, and a hydroxyl group-containing (meth) acrylate are combined is more preferable, and a copolymer in which butyl acrylate, methyl acrylate, glycidyl acrylate, and 2-hydroxyethyl acrylate are combined is further preferable.
The acrylic resin may be, for example, a resin obtained by copolymerizing 1 or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, and the like, in addition to (meth) acrylic acid ester.
The monomers constituting the acrylic resin may be 1 or 2 or more monomers. When the number of monomers constituting the acrylic resin is 2 or more, the combination and ratio thereof may be arbitrarily selected.
The polyarylate resin in the polymer component (a) may be a known polyarylate resin, for example, a resin essentially composed of a dihydric phenol and a dibasic acid such as phthalic acid or carboxylic acid by polycondensation. Among them, polycondensates of bisphenol A and phthalic acid, poly-4, 4' -isopropylidenediphenyl terephthalate/isophthalate copolymers, their derivatives and the like are preferable.
The polyvinyl acetal in the polymer component (a) may be a known polyvinyl acetal.
Among them, preferable polyvinyl acetals include, for example: polyvinyl formal, polyvinyl butyral, and the like, and more preferably polyvinyl butyral.
Examples of the polyvinyl butyral include polyvinyl butyrals having structural units represented by the following formulae (i) -1, (i) -2 and (i) -3.
[ chemical formula 1]
(wherein l, m and n are each independently an integer of 1 or more.)
The weight average molecular weight (Mw) of the polyvinyl acetal is preferably 5,000 ～ 200,000, more preferably 8,000 ～ 100,000. When the weight average molecular weight of the polyvinyl acetal is not less than the lower limit, the shape stability (stability with time during storage) of the thermosetting resin film can be easily improved. In addition, when the weight average molecular weight of the polyvinyl acetal is equal to or less than the upper limit value, the thermosetting resin film is liable to follow the uneven surface of the adherend, and for example, generation of voids or the like between the adherend and the thermosetting resin film is liable to be suppressed. Therefore, the semiconductor wafer has good coating properties on the bump formation surface, and the embedding property into the groove portion is easily improved.
From the viewpoints of film formability of the curable resin film and the head-like property of the bump head top, the glass transition temperature (Tg) of the polyvinyl acetal is preferably 40 to 80 ℃, more preferably 50 to 70 ℃.
Here, in the present specification, "the head-out property of the bump head top" means a property of penetrating a thermosetting resin film for forming a protective film when the thermosetting resin film is attached to a wafer with bumps, and is also referred to as penetrability of the bump head top.
The ratio of 3 or more monomers constituting the polyvinyl acetal may be arbitrarily selected.
The content of the polymer component (a) is preferably 2 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 3 to 15% by mass, based on the total amount of the active ingredients of the thermosetting resin composition.
The polymer component (A) may also belong to the thermosetting component (B). In the present invention, when the thermosetting resin composition contains such components belonging to both the polymer component (a) and the thermosetting component (B), it is considered that the thermosetting resin composition contains both the polymer component (a) and the thermosetting component (B).
[ thermosetting component (B) ]
The thermosetting resin film and the thermosetting resin composition contain a thermosetting component (B).
The thermosetting component (B) is a component for curing the thermosetting resin film to form a hard cured resin film.
The thermosetting component (B) may be used alone or in combination of 1 or more than 2. When the thermosetting component (B) is 2 or more, the combination and ratio thereof may be arbitrarily selected.
Examples of the thermosetting component (B) include: epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, and the like. Among them, epoxy thermosetting resins are preferable. When the thermosetting component (B) is an epoxy thermosetting resin, the protectiveness of the cured resin film and the head-out property of the top of the bump can be improved, and the warpage of the cured resin film can be suppressed.
The epoxy thermosetting resin contains an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy thermosetting resin may be used alone or in combination of at least 2 kinds. When the epoxy thermosetting resin is 2 or more, the combination and ratio thereof may be arbitrarily selected.
Epoxy resin (B1)
The epoxy resin (B1) is not particularly limited, and from the viewpoint of more easily exhibiting the effect of the present invention, it is preferable to use an epoxy resin that is solid at ordinary temperature (hereinafter also referred to as solid epoxy resin) in combination with an epoxy resin that is liquid at ordinary temperature (hereinafter also referred to as liquid epoxy resin).
In the present specification, "normal temperature" means 5 to 35 ℃, preferably 15 to 25 ℃.
The liquid epoxy resin is not particularly limited as long as it is liquid at ordinary temperature, and examples thereof include: bisphenol a type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, glycidyl ester type epoxy resins, biphenyl type epoxy resins, phenylene skeleton type epoxy resins, and the like. Among them, bisphenol a type epoxy resin is preferable.
The liquid epoxy resin may be used alone or in combination of 1 or more than 2. In the case where the liquid epoxy resin is 2 or more, the combination and ratio thereof may be arbitrarily selected.
The epoxy equivalent of the liquid epoxy resin is preferably 200 to 600g/eq, more preferably 250 to 550g/eq, still more preferably 300 to 500g/eq.
The solid epoxy resin is not particularly limited as long as it is solid at ordinary temperature, and examples thereof include: biphenyl type epoxy resins, bisphenol a type epoxy resins, bisphenol F type epoxy resins, o-cresol novolac epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, fluorene skeleton type epoxy resins, and the like. Among them, naphthalene-type epoxy resins and fluorene-skeleton type epoxy resins are preferable, and fluorene-skeleton type epoxy resins are more preferable.
The solid epoxy resin may be used alone or in combination of at least 1 kind and at least 2 kinds. When the solid epoxy resin is 2 or more, the combination and ratio thereof may be arbitrarily selected.
The epoxy equivalent of the solid epoxy resin is preferably 150 to 450g/eq, more preferably 150 to 400g/eq.
The ratio [ (x)/(y) ] of the content of the liquid epoxy resin (x) to the content of the solid epoxy resin (y) is preferably 0.2 to 10.0, more preferably 0.3 to 8.0, still more preferably 0.4 to 6.0, still more preferably 0.5 to 5.0 in terms of mass ratio. When the ratio [ (x)/(y) ] is within the above range, the elongation at break of the curable resin film after curing at 70℃can be easily adjusted to the above value or less.
The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30,000, more preferably 400 to 10,000, and even more preferably 500 to 3,000 from the viewpoints of curability of the thermosetting resin film, and strength and heat resistance of the cured resin film after curing.
Thermosetting agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
Examples of the thermosetting agent (B2) include compounds having 2 or more functional groups capable of reacting with an epoxy group in 1 molecule. Examples of the functional group include: the group obtained by acid anhydride treatment of a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid group is preferably a group obtained by acid anhydride treatment of a phenolic hydroxyl group, an amino group, or an acid group, and more preferably a phenolic hydroxyl group or an amino group.
Among the thermosetting agents (B2), as phenolic curing agents having phenolic hydroxyl groups, there may be mentioned, for example: polyfunctional phenol resins, diphenols, novolak-type phenol resins, dicyclopentadiene-type phenol resins, aralkyl phenol resins, and the like.
Among the thermosetting agents (B2), as amine-based curing agents having an amino group, there may be mentioned, for example: dicyandiamide (hereinafter may be abbreviated as "dic") and the like.
Among them, the phenolic curing agent having a phenolic hydroxyl group is preferable from the viewpoint of more easily exhibiting the effect of the present invention, and the novolac type phenolic resin is more preferable.
In the thermosetting agent (B2), for example, the number average molecular weight of the resin component such as a polyfunctional phenol resin, a novolak-type phenol resin, a dicyclopentadiene-type phenol resin, and an aralkyl-type phenol resin is preferably 300 to 30,000, more preferably 400 to 10,000, and further preferably 500 to 3,000.
In the thermosetting agent (B2), the molecular weight of the non-resin component such as bisphenol or dicyandiamide is not particularly limited, and is preferably 60 to 500, for example.
The thermosetting agent (B2) may be used alone or in combination of 1 or more than 2. When the amount of the thermosetting agent (B2) is 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the thermosetting resin composition, the content of the thermosetting agent (B2) is preferably 1 to 200 parts by mass, more preferably 5 to 150 parts by mass, still more preferably 10 to 100 parts by mass, still more preferably 15 to 77 parts by mass, relative to 100 parts by mass of the content of the epoxy resin (B1). By setting the content of the thermosetting agent (B2) to the above lower limit value or more, curing of the thermosetting resin film is easier. In addition, by setting the content of the thermosetting agent (B2) to the above-described upper limit value or less, the moisture absorption rate of the thermosetting resin film is reduced, and the reliability of the package obtained by using the thermosetting resin film is further improved.
In the thermosetting resin composition, the content of the thermosetting component (B) (the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is preferably 200 to 3000 parts by mass, more preferably 300 to 2000 parts by mass, still more preferably 400 to 1000 parts by mass, still more preferably 500 to 800 parts by mass, relative to 100 parts by mass of the content of the polymer component (a), from the viewpoint of improving the protective property of the cured resin film.
[ curing accelerator (C) ]
The thermosetting resin film and the thermosetting resin composition may contain a curing accelerator (C).
The curing accelerator (C) is a component for adjusting the curing speed of the thermosetting resin composition.
Preferable curing accelerators (C) include, for example: tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; imidazoles (imidazoles in which 1 or more hydrogen atoms are substituted with groups other than hydrogen atoms) such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributylphosphine, diOrganic phosphines such as phenylphosphine and triphenylphosphine (phosphine obtained by substituting 1 or more hydrogen atoms with an organic group); tetraphenyl group Tetraphenylborates such as tetraphenylborates and triphenylphosphine tetraphenylborates.
Among them, imidazoles are preferable, and 2-phenyl-4, 5-dihydroxymethylimidazole is more preferable, from the viewpoint of more easily exhibiting the effect of the present invention.
The curing accelerator (C) may be used alone or in combination of 1 or more than 2. When the curing accelerator (C) is 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the thermosetting resin composition, the content of the curing accelerator (C) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the content of the thermosetting component (B) when the curing accelerator (C) is used. By setting the content of the curing accelerator (C) to the above lower limit value or more, the effect of using the curing accelerator (C) can be more remarkably obtained. In addition, when the content of the curing accelerator (C) is equal to or less than the above-described upper limit value, for example, the effect of suppressing segregation caused by the movement of the curing accelerator (C) having a high polarity toward the adhesive interface with the adherend in the thermosetting resin film under high-temperature and high-humidity conditions is increased, and the reliability of the package obtained by using the thermosetting resin film is further improved.
[ Filler (D) ]
The thermosetting resin film and the thermosetting resin composition may contain a filler (D).
By containing the filler (D), the thermal expansion coefficient of the cured resin film obtained by curing the thermosetting resin film can be easily adjusted to an appropriate range, and the reliability of the package obtained by using the thermosetting resin film can be further improved. In addition, by incorporating the filler (D) in the thermosetting resin film, the moisture absorption rate of the cured resin film can be reduced and the heat dissipation property can be improved.
The filler (D) may be any of an organic filler and an inorganic filler, and is preferably an inorganic filler. As a preferable inorganic filler, for example, there may be mentioned: powders of silica, alumina, talc, calcium carbonate, titanium white, iron oxide red, silicon carbide, boron nitride, and the like; beads obtained by spheroidizing these inorganic fillers; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; glass fiber, and the like. Among them, from the viewpoint of more easily exhibiting the effect of the present invention, the inorganic filler is preferably silica or alumina.
The filler (D) may be used alone or in combination of at least 2 kinds.
When the filler (D) is 2 or more, the combination and ratio thereof may be arbitrarily selected.
The content of the filler (D) when the filler (D) is used is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, and even more preferably 10 to 30% by mass, based on the total amount of the active ingredients of the thermosetting resin composition, from the viewpoint of suppressing peeling of the cured resin film from the chip due to thermal expansion and thermal shrinkage.
The average particle diameter of the filler (D) is preferably 5nm to 1000nm, more preferably 5nm to 500nm, still more preferably 10nm to 300nm. The average particle diameter is obtained by measuring the outer diameters of 1 particle at a plurality of positions and obtaining the average value thereof.
[ energy ray-curable resin (E) ]
The thermosetting resin film and the thermosetting resin composition may contain an energy ray curable resin (E).
By incorporating the energy ray-curable resin (E) into the thermosetting resin film, the characteristics can be changed by irradiation with energy rays.
The energy ray-curable resin (E) is a resin obtained by polymerizing (curing) an energy ray-curable compound. Examples of the energy ray-curable compound include compounds having at least 1 polymerizable double bond in a molecule, and preferably acrylate compounds having a (meth) acryloyl group.
Examples of the acrylic acid ester compound include: (meth) acrylates having a chain 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; (meth) acrylic esters having a cyclic aliphatic skeleton such as dicyclopentyl di (meth) acrylic esters; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate; an oligoester (meth) acrylate; urethane (meth) acrylate oligomers; epoxy modified (meth) acrylates; polyether (meth) acrylates other than the polyalkylene glycol (meth) acrylates described above; itaconic acid oligomers, and the like.
The weight average molecular weight of the energy ray-curable compound is preferably 100 to 30,000, more preferably 300 to 10,000.
The energy ray-curable compound used for polymerization may be used alone or in combination of 1 or more than 2. When the energy ray-curable compound used for polymerization is 2 or more, the combination and ratio thereof may be arbitrarily selected.
When the energy ray-curable resin (E) is used, the content of the energy ray-curable resin (E) is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and even more preferably 10 to 85% by mass, based on the total amount of the active ingredients of the thermosetting resin composition.
[ photopolymerization initiator (F) ]
When the thermosetting resin film and the thermosetting resin composition contain the energy ray curable resin (E), the thermosetting resin film and the thermosetting resin composition may contain the photopolymerization initiator (F) in order to allow the polymerization reaction of the energy ray curable resin (E) to proceed efficiently.
Examples of the photopolymerization initiator (F) include: benzophenone, acetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid methyl ester, benzoin dimethyl ketal, 2, 4-diethylthioxanthone, 1-hydroxycyclohexylphenyl ketone, benzyl diphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzil, dibenzyl, diacetyl, 1, 2-diphenylmethane, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 2-chloroanthraquinone, and the like.
The photopolymerization initiator (F) may be used alone or in combination of 1 or more than 2. When the photopolymerization initiator (F) is 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the thermosetting resin composition, the content of the photopolymerization initiator (F) 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 (E).
[ additive (G) ]
The thermosetting resin film and the thermosetting resin composition may contain the additive (G) within a range not to impair the effects of the present invention. The additive (G) may be a known additive, and may be arbitrarily selected according to the purpose, and is not particularly limited.
As the preferable additive (G), for example, there may be mentioned: coupling agents, crosslinking agents, surfactants, plasticizers, antistatic agents, antioxidants, getters, and the like.
The additive (G) may be used alone or in combination of 1 or more than 2. In the case where the general-purpose additive (G) is 2 or more, the combination and ratio thereof may be arbitrarily selected.
The content of the additive (G) is not particularly limited, and may be appropriately selected according to the purpose.
[ solvent ]
The thermosetting resin composition preferably further contains a solvent.
The thermosetting resin composition containing the solvent becomes excellent in handleability.
The solvent is not particularly limited, and examples of a preferable solvent include: hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The solvent may be used alone or in combination of 1 or more than 2. In the case where the number of solvents is 2 or more, the combination and ratio thereof may be arbitrarily selected.
The solvent is preferably methyl ethyl ketone or the like from the viewpoint of more uniformly mixing the components contained in the thermosetting resin composition.
(Process for producing thermosetting resin composition)
The thermosetting resin composition can be prepared by blending the components constituting the composition.
The order of addition of the components at the time of blending is not particularly limited, and 2 or more components may be added simultaneously. In the case of using a solvent, the solvent may be mixed with any component other than the solvent to dilute the component in advance, or the solvent may be mixed with the component without diluting any component other than the solvent in advance.
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 or a paddle, a method of mixing by using a mixer, and a method of mixing by applying ultrasonic waves.
The temperature and time at the time of adding and mixing the components are not particularly limited as long as they do not cause deterioration of the components to be blended, and the temperature is preferably 15 to 30 ℃.
[ composite sheet ]
The curable resin film according to one embodiment of the present invention can be produced into a composite sheet having a laminated structure in which the curable resin film and the release sheet are laminated. By forming the composite sheet, the curable resin film can be stably supported and protected when the curable resin film is conveyed as a product package or conveyed in a manufacturing process of a semiconductor chip.
Fig. 1 is a schematic cross-sectional view showing the constitution of a composite sheet in one embodiment of the present invention, and fig. 2 is a schematic cross-sectional view showing the constitution of a composite sheet in another embodiment of the present invention.
The composite sheet 10 of fig. 1 includes a release sheet 1 and a curable resin film 2 provided on the release sheet 1. The release sheet 1 includes a base material 3 and a release layer 4, and the release layer 4 is provided so as to face the curable resin film 2.
The composite sheet 20 of fig. 2 includes a release sheet 11 and a curable resin film 12 provided on the release sheet 11. The release sheet 11 may have an intermediate layer 15 between the base material 13 and the release layer 14.
The laminate in which the base material 13, the intermediate layer 15, and the release layer 14 are laminated in this order is suitable for use as a back grinding sheet.
Hereinafter, each layer of the release sheet used for the composite sheet of the present invention will be described.
(substrate)
The base material is in the form of a sheet or film, and examples of the constituent materials thereof include the following various resins.
Examples of the resin constituting the base material include: polyethylene such as Low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE), and High Density Polyethylene (HDPE); polyolefin other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin; ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid ester copolymers, ethylene-norbornene copolymers and other ethylene copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride resins (resins obtained by using vinyl chloride as a monomer) such as polyvinyl chloride and vinyl chloride copolymers; a polystyrene; polycycloolefins; polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene 2, 6-naphthalate, and wholly aromatic polyesters having an aromatic ring group in all the structural units; 2 or more copolymers of the above polyesters; poly (meth) acrylates; polyurethane; a urethane acrylate; polyimide; a polyamide; a polycarbonate; a fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfone; polyetherketone, and the like.
The resin constituting the base material may be, for example, a polymer alloy such as a mixture of the above-mentioned polyester and a resin other than the above-mentioned polyester. In the polymer alloy of the above polyester and the resin other than the polyester, the amount of the resin other than the polyester is preferably a small amount.
The resin constituting the base material may be, for example, a crosslinked resin obtained by crosslinking 1 or 2 or more kinds of the resins exemplified above; modified resins such as ionomers of 1 or 2 or more of the resins exemplified previously are used.
The resin constituting the base material may be used alone or in combination of 1 or more than 2 kinds. When the number of the resins constituting the base material is 2 or more, the combination and ratio thereof may be arbitrarily selected.
The substrate may have only 1 layer (single layer) or may have a plurality of layers of 2 or more layers. In the case where the substrate is a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited.
The thickness of the base material is preferably 5 μm to 1,000 μm, more preferably 10 μm to 500 μm, still more preferably 15 μm to 300 μm, still more preferably 20 μm to 150 μm.
Here, "thickness of the substrate" refers to thickness of the entire substrate, for example, thickness of the substrate composed of a plurality of layers refers to total thickness of all layers constituting the substrate.
The substrate is preferably a substrate having high thickness accuracy, that is, a substrate in which variation in thickness is suppressed regardless of the location. Among the above-mentioned constituent materials, examples of such materials that can be used to construct the base material with high thickness accuracy include: polyethylene, polyolefin other than polyethylene, polyethylene terephthalate, polybutylene terephthalate, ethylene-vinyl acetate copolymer, and the like.
The base material may contain, in addition to the main constituent materials such as the above resin, various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer).
The substrate may be transparent or opaque, may be colored according to the purpose, or may be vapor-deposited with another layer.
The substrate can be produced by a known method. For example, the resin-containing base material can be produced by molding a resin composition containing the above resin.
(release layer)
The release layer has a function of imparting peelability to the release sheet. The release layer can be formed, for example, by using a cured product of a release layer-forming composition containing a release agent.
The release agent is not particularly limited, and examples thereof include: silicone resins, alkyd resins, acrylic resins, ethylene vinyl acetate copolymers, and the like. Among them, ethylene-vinyl acetate copolymer is preferable from the viewpoint of improving the head-out property of the bump head top and the peelability from the cured resin film.
The release layer may be 1 layer (single layer) or 2 or more layers. In the case where the release layer is a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited.
From the viewpoints of releasability and handleability, the thickness of the release layer is preferably 3 to 50 μm, more preferably 5 to 30 μm. Here, "thickness of the release layer" refers to the thickness of the entire release layer, for example, the thickness of the release layer composed of a plurality of layers refers to the total thickness of all layers constituting the release layer.
(intermediate layer)
The intermediate layer is sheet-like or film-like, and the constituent material thereof may be appropriately selected according to the purpose, and is not particularly limited. For example, in the case where the purpose is to suppress deformation of the cured resin film due to reflection of the shape of the bump present on the semiconductor surface on the protective film covering the semiconductor surface, urethane (meth) acrylate and the like are given as preferable constituent materials of the intermediate layer from the viewpoints of high concave-convex following property and further improvement of adhesion of the intermediate layer.
The intermediate layer may be 1 layer (single layer) or 2 or more layers. In the case where the intermediate layer is a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited.
The thickness of the intermediate layer can be appropriately adjusted in accordance with the height of the bump on the semiconductor surface to be protected, and is preferably 50 μm to 600 μm, more preferably 70 μm to 500 μm, and even more preferably 80 μm to 400 μm, from the viewpoint of being able to easily absorb the influence of the bump having a high height. Here, the "thickness of the intermediate layer" refers to the thickness of the entire intermediate layer, and for example, the thickness of the intermediate layer composed of a plurality of layers refers to the total thickness of all the layers constituting the intermediate layer.
(method for producing composite sheet)
The composite sheet can be manufactured by sequentially laminating the above layers in a corresponding positional relationship.
For example, in the case of laminating a release layer or an intermediate layer on a substrate in the production of a composite sheet, the release layer or the intermediate layer may be laminated by applying a composition for forming a release layer or a composition for forming an intermediate layer on the substrate, and drying or irradiating energy rays as necessary.
Examples of the coating method include: spin coating, spray coating, bar coating, blade coating, roll coating, knife coating, blade coating, die coating, gravure coating, and the like.
On the other hand, for example, in the case where a curable resin film is further laminated on a release layer formed by lamination on a substrate, the curable resin film may be directly formed by applying a thermosetting resin composition on the release layer.
Similarly, when a release layer is further laminated on an intermediate layer formed by lamination on a substrate, the release layer may be directly formed by applying a composition for forming a release layer on the intermediate layer.
In this way, when a laminated structure of 2 continuous layers is formed using an arbitrary composition, a new layer can be formed by further coating a composition on 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 layer to be formed on the opposite side to the side to be in contact with the above release film is bonded to the exposed surfaces of the remaining layers to be formed, thereby forming a continuous 2-layer laminated structure. In this case, the composition is preferably applied to the release treated surface of the release film. The release film may be removed as needed after the laminated structure is formed.
[ method for manufacturing semiconductor chip ]
The method for manufacturing a semiconductor chip of the present invention generally includes: the method further includes a step (S1) of preparing a wafer for manufacturing semiconductor chips, a step (S2) of adhering a curable resin film, a step (S3) of curing the curable resin film, and a step (S4) of singulating the curable resin film, and further includes: and grinding the back surface of the wafer for manufacturing the semiconductor chip (S-BG).
Specifically, the method for manufacturing a semiconductor chip of the present invention includes the following steps (S1) to (S4) in this order.
Step (S1): a step of preparing a wafer for semiconductor chip production having grooves as lines to divide formed in a semiconductor wafer having a bump formation surface provided with bumps so that the bump formation surface does not reach the back surface
Step (S2): pressing and adhering the curable resin film to the bump formation surface of the semiconductor chip manufacturing wafer, coating the bump formation surface of the semiconductor chip manufacturing wafer with the curable resin film, and embedding the curable resin film in the groove of the semiconductor chip manufacturing wafer
Step (S3): a step of curing the curable resin film to obtain a wafer for producing semiconductor chips having a cured resin film
Step (S4): a step of singulating the wafer for producing semiconductor chips with the cured resin film along the predetermined dividing lines to obtain semiconductor chips having at least the bump formation surfaces and the side surfaces covered with the cured resin film
The following step (S-BG) is included after the step (S2) and before the step (S3), after the step (S3) and before the step (S4), or in the step (S4).
Step (S-BG): grinding the back surface of the wafer for manufacturing semiconductor chips
In the method for manufacturing a semiconductor chip according to the present invention, when the curable resin film is buried in the groove portion formed in the wafer for manufacturing a semiconductor chip, and the curable resin film is cured and the formed curable resin film is cut along the line to be cut, deformation due to elongation of the curable resin film caused by frictional heat and generation of cutting scraps can be suppressed. Therefore, deformation of the cut surface of the semiconductor wafer and adhesion of the cutting chips to the cut surface are less likely to occur, and a semiconductor chip excellent in processing quality can be obtained.
In the method for manufacturing a semiconductor chip according to the present invention, when the curable resin film is embedded in the groove portion formed in the wafer for manufacturing a semiconductor chip and the curable resin film is cured and the formed curable resin film is cut along the line to be cut, only the curable resin film is cut without cutting the wafer for manufacturing a semiconductor chip when the dicing blade is used for cutting. Therefore, the effect of removing the chips of the cured resin film as in the case of cutting the semiconductor chip-producing wafer together with the cured resin film, or the effect of projecting the abrasive grains in the case of cutting the semiconductor chip-producing wafer by the dicing blade does not occur, and the processing quality of the cut surface of the cured resin film formed by the dicing blade is easily degraded. However, in the present invention, since the elongation at break at 70 ℃ after curing of the curable resin film is adjusted to 85% or less, a semiconductor chip excellent in processing quality can be obtained without causing degradation in processing quality of the cut surface of the cured resin film formed by the dicing blade.
Further, by the manufacturing method including the above steps, a semiconductor chip having excellent strength and being hardly peeled off from the cured resin film serving as the protective film can be obtained in which not only the bump formation surface but also the side surfaces are covered with the cured resin film.
Here, "coated" means that a cured resin film is formed on at least the bump formation surface and the side surface of 1 semiconductor chip along the shape of the semiconductor chip.
Hereinafter, the method for manufacturing a semiconductor chip according to the present invention will be described in detail in terms of steps.
In the following description, the "semiconductor chip" is also simply referred to as a "chip" and the "semiconductor wafer" is also simply referred to as a "wafer".
The curable resin film (curable resin film of the present invention) used to form the curable resin film serving as the protective film on both the bump formation surface and the side surface of the semiconductor chip is also referred to as "first curable resin film (X1)". Further, a cured resin film formed by curing the "first curable resin film (X1)" is also referred to as a "first cured resin film (r 1)". The curable resin film used to form the cured resin film as the protective film on the surface (back surface) of the semiconductor chip opposite to the bump formation surface is also referred to as "second curable resin film (X2)". Further, the cured resin film formed by curing the "second curable resin film (X2)" is also referred to as "second cured resin film (r 2)".
The composite sheet for forming the first cured resin film (r 1) as the protective film on both the bump formation surface and the side surface of the semiconductor chip is also referred to as a "first composite sheet (α1)". The "first composite sheet (α1)" has a laminated structure in which the "first release sheet (Y1)" and the "first curable resin film (X1)" are laminated.
In addition, a composite sheet for forming a second cured resin film (r 2) as a protective film on the back surface of the semiconductor chip is also referred to as a "second composite sheet (α2)". The "second composite sheet (α2)" has a laminated structure in which the "second release sheet (Y2)" and the "second curable resin film (X2)" are laminated.
[ procedure (S1) ]
Fig. 3 shows a schematic cross-sectional view of an example of the semiconductor wafer prepared in the step (S1).
In step (S1), a semiconductor chip manufacturing wafer 30 is prepared, and the semiconductor chip manufacturing wafer 30 has grooves 23 as lines to divide formed in the bump formation surface 21a of the semiconductor wafer 21 having the bump formation surface 21a of the bump 22 so as not to reach the back surface 21 b.
The shape of the bump 22 is not particularly limited as long as it can be fixed in contact with an electrode or the like on a substrate for mounting a chip, and may be any shape. For example, in fig. 3, the projections 22 are spherical, but the projections 22 may be spheroids of revolution. The spheroid may be, for example, a spheroid extending in a vertical direction with respect to the bump formation surface 21a of the wafer 21, or a spheroid extending in a horizontal direction with respect to the bump formation surface 21a of the wafer 21. The bump 22 may have a pillar shape.
The height of the bump 22 is not particularly limited, and may be appropriately changed according to the design requirements.
As an example, 30 μm to 300 μm, preferably 60 μm to 250 μm, more preferably 80 μm to 200 μm.
The "height of the bump 22" refers to a height of a portion located at the highest position from the bump formation surface 21a when focusing on 1 bump.
The number of the bumps 22 is not particularly limited, and may be appropriately changed according to the design requirements.
The wafer 21 is, for example, a semiconductor wafer having circuits such as wirings, capacitors, diodes, and transistors formed on the surface thereof. The material of the wafer is not particularly limited, and examples thereof include: silicon wafers, silicon carbide wafers, compound semiconductor wafers, glass wafers, sapphire wafers, and the like.
The size of the wafer 21 is not particularly limited, but is usually 8 inches (diameter 200 mm) or more, preferably 12 inches (diameter 300 mm) or more, from the viewpoint of improving the batch processing efficiency. The shape of the wafer 21 is not limited to a circular shape, and may be square, rectangular, or the like, for example. In the case of square wafers, the length of the longest side is preferably equal to or greater than the above-described dimension (diameter) in terms of improving the lot processing efficiency with respect to the dimension of the wafer 21.
The thickness of the wafer 21 is not particularly limited, but is preferably 100 μm to 1,000 μm, more preferably 200 μm to 900 μm, and even more preferably 300 μm to 800 μm, from the viewpoint of easily suppressing warpage associated with shrinkage when curing the curable resin film, and reducing the time required for back grinding by suppressing the grinding amount of the back surface 21b of the wafer 21 in the subsequent step.
The bump formation surface 21a of the semiconductor chip manufacturing wafer 30 prepared in the step (S1) is formed with a plurality of grooves 23 in a lattice shape as lines for dividing when the semiconductor chip manufacturing wafer 30 is singulated. The plurality of grooves 23 are scribe grooves formed by the dicing method (Dicing Before Grinding) and are formed to a depth shallower than the thickness of the wafer 21 so that the deepest portions of the grooves 23 do not reach the back surface 21b of the wafer 21. The plurality of grooves 23 may be formed by dicing using a conventionally known wafer dicing apparatus or the like having dicing blades.
The plurality of grooves 23 may be formed so that the semiconductor chip to be manufactured has a desired size and shape. The size of the semiconductor chip is generally about 0.5mm×0.5mm to 1.0mm×1.0mm, but is not limited to this size.
The width of the groove 23 is preferably 10 μm to 2,000 μm, more preferably 30 μm to 1,000 μm, still more preferably 40 μm to 500 μm, still more preferably 50 μm to 300 μm, from the viewpoint of improving the embeddability of the curable resin film.
The depth of the groove 23 can be adjusted according to the thickness of the wafer to be used and the required chip thickness, and is preferably 30 μm to 700 μm, more preferably 60 μm to 600 μm, and still more preferably 100 μm to 500 μm.
The wafer 30 for manufacturing semiconductor chips prepared in the step (S1) is supplied to the step (S2).
[ procedure (S2) ]
Fig. 4 shows an outline of the step (S2).
In step (S2), the first curable resin film (X1) is pressed against and bonded to the bump formation surface 21a of the semiconductor chip manufacturing wafer 30.
Here, from the viewpoint of operability, the first curable resin film (X1) may be used as a first composite sheet (α1) having a laminated structure in which a first release sheet (Y1) and the first curable resin film (X1) are laminated. When the first composite sheet (α1) is used, the first curable resin film (X1) of the first composite sheet (α1) is pressed against and bonded to the bump formation surface 21a of the semiconductor chip manufacturing wafer 30 as a bonding surface.
In the step (S2), as shown in fig. 4, the bump formation surface 21a of the semiconductor chip manufacturing wafer 30 is covered with the first curable resin film (X1), and the first curable resin film (X1) is buried in the groove portion 23 formed in the semiconductor chip manufacturing wafer 30.
From the viewpoint of the satisfactory embedding of the first curable resin film (X1) into the groove 23, the pressing force at the time of adhering the first curable resin film (X1) to the wafer 30 for semiconductor chip production is preferably 1kPa to 200kPa, more preferably 5kPa to 150kPa, still more preferably 10kPa to 100kPa.
The pressing force at the time of bonding the first curable resin film (X1) to the semiconductor chip manufacturing wafer 30 may be appropriately changed from the initial stage to the final stage of bonding. For example, from the viewpoint of improving the embeddability of the first curable resin film (X1) into the groove portion 23, it is preferable to make the pressing force low at the initial stage of adhesion and gradually increase the pressing force.
In addition, when the first curable resin film (X1) is bonded to the wafer 30 for semiconductor chip production, in the case where the first curable resin film (X1) is a thermosetting resin film, heating is preferably performed in order to improve the embeddability of the first curable resin film (X1) into the groove portion 23.
The specific heating temperature (sticking temperature) is preferably 50 to 150 ℃, more preferably 60 to 130 ℃, and even more preferably 70 to 110 ℃.
The heat treatment performed on the first curable resin film (X1) is not included in the curing treatment of the first curable resin film (X1).
In addition, when the first curable resin film (X1) is bonded to the wafer 30 for semiconductor chip production, it is preferable to perform the bonding in a reduced pressure environment. Thus, the groove 23 is under negative pressure, and the first curable resin film (X1) is easily spread over the entire groove 23. As a result, the first curable resin film (X1) has better embeddability into the groove 23. The specific pressure in the reduced pressure environment is preferably 0.001kPa to 50kPa, more preferably 0.01kPa to 5kPa, and still more preferably 0.05kPa to 1kPa.
[ procedure (S3) ]
Fig. 5 shows an outline of the step (S3).
In step (S3), the first curable resin film (X1) is cured to obtain the semiconductor chip manufacturing wafer 30 having the first cured resin film (r 1).
The first curable resin film (r 1) formed by curing the first curable resin film (X1) is stronger than the first curable resin film (X1) at normal temperature. Therefore, by forming the first cured resin film (r 1), the bump neck portion is well protected.
The first curable resin film (X1) may be cured by either one of thermal curing and curing by irradiation with energy rays, depending on the kind of the curable component contained in the first curable resin film (X1).
In the present specification, the term "energy ray" refers to a ray having energy quanta in an electromagnetic wave or a charged particle beam, and examples thereof include ultraviolet rays, electron beams, and the like, and ultraviolet rays are preferable.
As the conditions for performing the heat curing, the curing temperature is preferably 90 to 200℃and the curing time is preferably 1 to 3 hours.
The conditions for curing by irradiation with energy rays may be appropriately set according to the type of energy rays used. For example, in the case of using ultraviolet rays, the illuminance is preferably 170mw/cm 2 ～250mw/cm 2 The light quantity is preferably 300mJ/cm 2 ～3,000mJ/cm 2 。
Here, in the process of forming the first curable resin film (r 1) by curing the first curable resin film (X1), the first curable resin film (X1) is preferably a thermosetting resin film from the viewpoint of removing bubbles or the like that may enter when the groove portion 23 is buried with the first curable resin film (X1) in the step (S2).
[ procedure (S4) ]
Fig. 6 shows an outline of the step (S4).
In step (S4), the portion of the first cured resin film (r 1) of the semiconductor chip manufacturing wafer 30 having the first cured resin film (r 1) formed in the groove 23 is cut along the predetermined line for dicing.
Since the first cured resin film (r 1) is formed by curing the curable resin film of the present invention, the elongation at break of the first cured resin film (r 1) at 70 ℃ satisfies 85% or less. Therefore, in the step (S4), when the portion of the first cured resin film (r 1) formed in the groove portion 23 is cut along the line to be cut, deformation and generation of cutting scraps due to the expansion of the first cured resin film (r 1) caused by frictional heat can be suppressed. Therefore, deformation of the cut surface of the wafer and adhesion of the cutting chips to the cut surface are less likely to occur, and a semiconductor chip excellent in processing quality can be obtained.
The cutting is performed by knife cutting. Thus, the semiconductor chip 40 having at least the bump formation surface 21a and the side surfaces covered with the first cured resin film (r 1) can be obtained.
Since the bump formation surface 21a and the side surfaces of the semiconductor chip 40 are covered with the first cured resin film (r 1), excellent strength is provided. Since the bump formation surface 21a and the side surface are continuously covered with the first cured resin film (r 1) without any gap, the junction surface (interface) between the bump formation surface 21a and the first cured resin film (r 1) is not exposed on the side surface of the semiconductor chip 40. In the joint surface (interface) between the bump formation surface 21a and the first cured resin film (r 1), the exposed portion exposed on the side surface of the semiconductor chip 40 is likely to become a starting point for film peeling. Since the exposed portion is not present in the semiconductor chip 40 of the present invention, film peeling due to the exposed portion is less likely to occur during and after the process of manufacturing the semiconductor chip 40 by cutting the semiconductor chip manufacturing wafer 30. Therefore, the semiconductor chip 40 in which peeling of the first cured resin film (r 1) as the protective film is suppressed can be obtained.
In the step (S4), when the portion of the first cured resin film (r 1) of the semiconductor chip manufacturing wafer 30 having the first cured resin film (r 1) formed in the groove 23 is cut along the line to be divided, the first cured resin film (r 1) is preferably transparent. By making the first cured resin film (r 1) transparent, the semiconductor wafer 21 can be seen through, and thus the visibility of the dividing lines can be ensured. Therefore, cutting along the line to be cut is easy.
[ procedure (S-BG) ]
Fig. 7 shows an outline of the process (S-BG).
In the step (S-BG), as shown in fig. 7 (1-a), first, the back surface 21b of the semiconductor chip manufacturing wafer 30 is ground in a state where the first composite sheet (α1) is attached. "BG" in fig. 7 refers to back grinding (back grinding). Next, as shown in fig. 7 (1-b), the first separator (Y1) is separated from the first composite sheet (α1).
The grinding amount at the time of grinding the back surface 21b of the wafer 30 for semiconductor chip production may be an amount at least exposing the bottom of the groove 23 of the wafer 30 for semiconductor chip production, and the first curable resin film (X1) or the first curable resin film (r 1) embedded in the groove 23 may be further ground together with the wafer 30 for semiconductor chip production.
The step (S-BG) may be performed after the step (S2) and before the step (S3), may be performed after the step (S3) and before the step (S4), or may be performed in the step (S4). Among them, from the viewpoint of more easily exhibiting the effect of the present invention, it is preferable to perform the step (S3) after the step (S4) or the step (S4).
[ procedure (T) ]
In one embodiment of the method for manufacturing a semiconductor chip of the present invention, the method preferably further includes the following step (T).
Step (T): a step of forming a second cured resin film (r 2) on the back surface of the wafer for producing semiconductor chips
According to the manufacturing method of the above embodiment, the semiconductor chip 40 in which at least the bump formation surface 21a and the side surface are covered with the first cured resin film (r 1) can be obtained. But the back surface of the semiconductor chip 40 is exposed. Therefore, the above-described step (T) is preferably performed in view of further improving the strength of the semiconductor chip 40 by protecting the back surface of the semiconductor chip 40.
More specifically, the above-mentioned step (T) preferably includes the following step (T1) and the following step (T2) in this order.
Step (T1): a step of adhering a second curable resin film (X2) to the back surface of the wafer for producing semiconductor chips
Step (T2): a step of forming a second curable resin film (r 2) by curing the second curable resin film (X2)
In the step (T1), a second composite sheet (α2) having a laminated structure in which a second release sheet (Y2) and a second curable resin film (X2) are laminated may be used. Specifically, the step (T1) is preferably a step of adhering a second composite sheet (α2) having a laminated structure in which a second release sheet (Y2) and a second curable resin film (X2) are laminated to the back surface of the wafer for producing semiconductor chips with the second curable resin film (X2) as an adhesive surface.
In this case, the timing of peeling the second separator (Y2) from the second composite sheet (α2) may be between the step (T1) and the step (T2), or may be after the step (T2).
Here, when the second composite sheet (α2) is used in the step (T1), the release sheet (Y2) of the second composite sheet (α2) preferably has a function as a dicing sheet while supporting the second curable resin film (X2).
In the step (S4), the second composite sheet (α2) is adhered to the back surface 21b of the semiconductor chip manufacturing wafer 30 having the first cured resin film (r 1), so that the second release sheet (Y2) functions as a dicing sheet when dicing is performed, and dicing is easily performed.
Here, when the step (S3) is performed after the step (S-BG), the step (T1) may be performed before the step (S3), and then the step (S3) and the step (T2) may be performed simultaneously. That is, the first curable resin film (X1) and the second curable resin film (X2) can be simultaneously cured at one time. This can reduce the number of curing treatments.
[ procedure (U) ]
In one embodiment of the method for manufacturing a semiconductor chip of the present invention, the method may further include the following step (U).
Step (U): removing the first cured resin film (r 1) including the top of the bump or the first cured resin film (r 1) attached to a part of the top of the bump to expose the top of the bump
The exposure process for exposing the top of the bump includes, for example, etching processes such as wet etching process and dry etching process.
Here, the dry etching process includes, for example, a plasma etching process and the like.
In the case where the top of the bump is not exposed to the surface of the protective film, the exposure treatment may be performed for the purpose of causing the protective film to recede to be exposed to the top of the bump.
The timing of the step (U) is not particularly limited as long as the first cured resin film (r 1) is exposed, and is preferably a state after the step (S3) and before the step (S4) without the release sheet (Y1) and the back grinding sheet being adhered.
[ semiconductor chip ]
The semiconductor chip of the present invention has a bump formation surface provided with bumps, and the semiconductor chip of the present invention has a cured resin film obtained by curing the curable resin film of the present invention on both the bump formation surface and the side surface.
The semiconductor chip of the present invention can be obtained by cutting and singulating a cured resin film embedded in a groove portion formed in a wafer for manufacturing a semiconductor chip along a line to be cut. Since the cured resin film is a cured product of the curable resin film, deformation and generation of cutting scraps due to elongation of the cured resin film caused by frictional heat can be suppressed when the cured resin film is cut along a line to cut. Therefore, the semiconductor chip of the present invention is less likely to be deformed and the adhesion of the cutting chips is less likely to occur, and the processing quality is excellent.
Examples
The present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.
1. Raw material for producing curable resin film-forming composition
The raw materials used for producing the curable resin film-forming composition are shown below.
(1) Polymer component (A)
(A) -1: polyvinyl butyral having a structural unit represented by the following formula (i) -1, (i) -2 and (i) -3 (S-LEC BL-10, manufactured by Seattle chemical Co., ltd.); weight average molecular weight 25000, glass transition temperature 59 ℃ C.)
(A) -2: polyarylate (Unifin (registered trademark) M-2040 manufactured by Unitika Co., ltd.)
[ chemical formula 2]
(wherein, l 1 About 28, m 1 Is 1 to 3, n 1 Is an integer of 68 to 74. )
(thermosetting component (B))
(2) Epoxy resin (B1)
[ liquid epoxy resin ]
(B1) -1: liquid modified bisphenol A type epoxy resin (EPICLON EXA-4850-150", manufactured by DIC Co., ltd.," number average molecular weight 900 ", epoxy equivalent 450 g/eq)
[ solid epoxy resin ]
(B1) -2: naphthalene type epoxy resin (EPICLON HP-4710 manufactured by DIC Co., ltd., "epoxy equivalent 170 g/eq)
(B1) -3: naphthalene type epoxy resin (EPICLON HP-5000, manufactured by DIC Co., ltd., "epoxy equivalent 252 g/eq)
(B1) -4: fluorene skeleton type epoxy resin (OGSOL CG500, manufactured by Osaka Gas Chemicals Co., ltd., "epoxy equivalent 300 g/eq)
(3) Thermosetting agent (B2)
(B2) -1: o-cresol novolak resin (PHENOLITE KA-1160, manufactured by DIC Co., ltd., "hydroxyl equivalent 117 g/eq)
(4) Curing accelerator (C)
(C) -1: 2-phenyl-4, 5-dihydroxymethylimidazole (CUREZOL 2PHZ-PW manufactured by Sichuangchi chemical industry Co., ltd.)
(5) Filler material (D)
(D) -1: spherical silica modified with epoxy group (Admanno YA050C-MKK, manufactured by Admatechs Co., ltd., "average particle size 50 nm)
(6) Additive (G)
(G) -1: surfactant (acrylic Polymer, BYK-361N manufactured by BYK Co.)
(G) -2: silicone oil (aralkyl modified silicone oil, manufactured by Momentive Performance Materials Japan company "XF 42-334")
2. Examples 1 to 5 and comparative examples 1 and 2
2-1 example 1
(1) Production of thermosetting resin film-forming composition (1)
The polymer component (a) -2 (100 parts by mass), the epoxy resin (B1) -1 (295 parts by mass), the epoxy resin (B1) -4 (210 parts by mass), the thermosetting agent (B2) -1 (162 parts by mass), the curing accelerator (C) -1 (2 parts by mass), the filler (D) -1 (199 parts by mass), the additive (G) -1 (22 parts by mass), and the additive (G) -2 (2 parts by mass) were dissolved or dispersed in methyl ethyl ketone, and stirred at 23 ℃ to obtain the thermosetting resin film-forming composition (1) having a total concentration of all the components except the solvent of 60% by mass. The amounts of the components other than the solvent shown here are all amounts of the target compound containing no solvent.
(2) Production of thermosetting resin film
A release film (SP-PET 381031, manufactured by Lindeke Co., ltd., thickness: 38 μm) obtained by subjecting one surface of a polyethylene terephthalate film to release treatment by silicone treatment was coated with the composition (1) obtained above, and the resultant film was dried by heating at 120℃for 2 minutes, thereby forming a thermosetting resin film having a thickness of 45. Mu.m.
2-2. Examples 2 to 5 and comparative examples 1 and 2
A thermosetting resin film having a thickness of 45 μm was formed in the same manner as in example 1 except that either one or both of the types and the blending amounts of the blending components at the time of producing the thermosetting resin film-forming composition (1) were changed so that the types and the content of the components contained in the thermosetting resin film-forming composition (1) were as shown in table 1 described below.
Note that the description of "-" in table 1, which contains a component in a column, means that the thermosetting resin film-forming composition does not contain the component.
3. Evaluation
The thermosetting resin film obtained above was used for the following evaluation. The results are shown in Table 2.
3-1 calculation of crosslink Density
The crosslink density is calculated by the following formula.
[ mathematics 1]
3-2 measurement of elongation at break (T), energy at break (E) and calculation of TXE
5 thermosetting resin films having a thickness of 45 μm were laminated at 60℃to prepare a laminated film having a thickness of 225. Mu.m. The laminate film was cured by heating at 130℃under a pressure of 0.5MPa for 240 minutes, and then placed on a dicing tape ("D-676H" manufactured by Leideco Co., ltd.), followed by grinding using a dicing apparatus ("DFD 6362" manufactured by DISCO Co., ltd.) at a rotational speed of 30000rpm, a feed speed of 10 mm/sec and a cut mark amount of 20. Mu.m, to prepare a test piece having a width of 3mm and a length of 100 mm.
The test piece was set in a Tensilon universal tester (RTG-1210, orientec Co., ltd.) equipped with a constant temperature bath, and a constant temperature bath for a tester (TKC-R3T-G-S, orientec Co., ltd.) so that the length between chucks was 50mm, and the elongation at break (T) and the breaking energy (E) were measured at a temperature of 70℃and a speed of 200 mm/min. T.times.E is calculated from the values of the elongation at break (T) and the energy at break (E) obtained.
3-3 measurement of Gc1 and Gc300 of curable resin film, calculation of X value
20 thermosetting resin films having a thickness of 45 μm were produced. Next, these thermosetting resin films were laminated, and the obtained laminated film was cut into a disk shape having a diameter of 25mm, thereby producing a test piece of a thermosetting resin film having a thickness of 900 μm.
The test piece was fixed to the installation site by previously incubating the installation site of the test piece in the viscoelasticity measuring apparatus (MCR 301 manufactured by Anton Paar corporation) at 80 ℃, placing the test piece of the thermosetting resin film obtained above on the installation site, and abutting the measuring jig against the upper surface of the test piece.
Then, the strain applied to the test piece was gradually increased in the range of 0.01% to 1000% at a temperature of 90℃and a measurement frequency of 1Hz, and the storage modulus Gc of the test piece was measured. Then, the X value is calculated from the measured values of Gc1 and Gc 300.
3-4 evaluation of the embeddability into the groove portion and exudation from the wafer edge portion
(1) Preparation of wafer for semiconductor chip fabrication
As a wafer for manufacturing a semiconductor chip, a 12-inch silicon wafer (wafer thickness 750 μm) obtained by half-cutting a predetermined dividing line was used. The width of the half-cut portion (width of the groove portion) of the silicon wafer was 60. Mu.m, and the depth of the groove was 230. Mu.m.
(2) Evaluation method
One surface of a thermosetting resin film having a thickness of 45 μm was pressed and bonded to the front surface side (half-cut formation surface) of the wafer for semiconductor chip production under the following conditions.
Paste device: BG tape lamination machine (RAD-3510F/8 manufactured by Lindeke Co., ltd.)
Paste pressure: 0.5MPa
Paste time: 43 seconds
Paste speed: 7 mm/sec
Paste temperature: 80 DEG C
Roll sticking height: -200mm
Then, the wafer for manufacturing a semiconductor chip to which the thermosetting resin film was attached was heated at 130℃and a pressure of 0.5MPa for 4 hours to be cured, thereby forming a cured resin film. Then, the semiconductor chip-producing wafer was cut from the half-cut formation surface toward the back surface, and the cured resin film was observed for the embeddability into the grooves of the half-cut portion by an optical microscope (VHX-100 manufactured by KEYENCE corporation). In addition, the presence or absence of bleeding of the cured resin film from the wafer edge was visually observed.
The evaluation criteria for the embeddability are as follows.
S: the cured resin film was not deformed in shape, and the embeddability was the best.
A: although a slight deformation in the shape of the cured resin film was observed in the vicinity of the inlet of the groove portion, the embeddability was good.
B: poor embeddability.
3-5 evaluation of processing quality and confirmation of the presence or absence of retentate
5 thermosetting resin films having a thickness of 45 μm were laminated at 60℃and then cut into a size of 5cm in the longitudinal direction and 5cm in the transverse direction, whereby a laminated film having a thickness of 225 μm was prepared. The laminate film was cured by heating at 130℃and a pressure of 0.5MPa for 240 minutes, and then adhered to a dicing tape (product of Wandeke Co., ltd. "D-676H"). Next, the surface of the laminate film on the opposite side to the dicing tape-applied surface was ground using a dicing apparatus (DFD 6362, manufactured by DISCO Co., ltd., blade: ZH05-SD1500-N1-50-27HECC, blade width 0.03 mm) at a rotation speed of 30000rpm, a feed speed of 30 mm/sec, and a cut mark amount of 20. Mu.m, and a resin-only chip (hereinafter also simply referred to as a chip) having a quadrangular shape of 2mm in the longitudinal direction and 2mm in the transverse direction was singulated.
The surface of the laminate film on which the dicing lines were formed (the surface opposite to the dicing tape-adhering surface) was observed with a digital microscope (VHX-7000, manufactured by KEYENCE corporation) to confirm the presence or absence of the retentate at the dicing lines. The results are shown in table 2 on the "retentate surface side".
Next, the film was irradiated with light at an illuminance of 230mW/cm from the back surface (dicing tape-attached surface) of the laminated film using a UV irradiation device (RAD-2000F/12, manufactured by Lindeke Co., ltd.) 2 Light quantity 190mJ/cm 2 After irradiating ultraviolet rays, the surface of the laminate film (the surface opposite to the dicing tape-attached surface) was transferred to a semiconductor processing tape (product of "D-210" manufactured by lindeke corporation). The chips surrounded by the dicing lines were observed from the back surface (dicing tape-attached surface) of the laminated film transferred to the semiconductor processing tape by means of a digital microscope (VHX-7000, manufactured by KEYENCE corporation), and the presence or absence of deformation of the chips due to the retentate was evaluated by the following criteria. The ratio of the deformation of the chip was calculated by the following formula. The results are shown in Table 2 on the "back side of the retentate".
[ math figure 2]
In the above formula, ha is the blade width (mm) of the blade used for cutting, and is 0.03mm in this evaluation. Hb is the kerf width (mm) of the dicing line measured by the following procedure.
The distance between the chips (referred to as kerf width) between the chip singulated by the dicing apparatus and the chip adjacent to one side of the chip was observed by a digital microscope, and the distance at the narrowest point was measured. The procedure was repeated for the amount of 4 chips, and an average value (mm) was calculated.
[ evaluation criterion of the rear surface of laminated film ]
0: no distortion was observed at the dicing lines of the chip.
1: deformation of 1% or more and less than 20% was observed at the dicing line of the chip.
2: deformation of 20% or more and less than 50% was observed at the dicing line of the chip.
3: deformation of 50% or more was observed in the dicing line of the chip.
Next, the laminate film was irradiated with light at an illuminance of 230mW/cm from the semiconductor processing tape side using a UV irradiation apparatus (RAD-2000F/12, manufactured by Lindeke Co., ltd.) 2 Light quantity 190mJ/cm 2 And then pick up the chip surrounded by the dicing lines. The side surface of the chip was observed from a direction at an angle of 45 ° to the vertical direction with respect to the upper surface of the chip using a scanning electron microscope (SEM, manufactured by KEYENCE corporation, "VE-9700"), and the processing quality was evaluated based on the following criteria. The ratio of contamination at the corner of the chip and the ratio of contamination at the side of the chip were calculated by the following formula.
[ math 3]
In the above formula, ta is the thickness (μm) of the singulated chip, and 225 μm was used in this evaluation. Tb is an average value (. Mu.m) obtained by measuring the width (perpendicular to the chip surface) of the region where the chip or the retentate is adhered in the corner of the singulated chip of 4 chips.
[ mathematics 4]
In the above formula, ta is the thickness (μm) of the singulated chip, and 225 μm was used in this evaluation. Tc is an average value (. Mu.m) obtained by measuring the width of the region (perpendicular to the chip surface) where the chip or the retentate was cut off in the side surface of the singulated chip of 4 chips.
[ evaluation of chip corner and side surfaces ]
Evaluation (1): the side surface of the chip was observed to confirm the presence or absence of the protrusion caused by the adhesion of the chip or the retentate.
Evaluation (2): contamination of the corners of the chip
0: no protrusion caused by cutting chips or retentate was observed at the corners of the chip.
1: protrusions caused by cutting chips or retentate were observed at the corners of the chip, and the protrusions contaminated more than 1% and less than 20% of the corners of the chip.
2: protrusions caused by cutting chips or retentate were observed at the corners of the chip, which contaminated more than 20% and less than 50% of the corners of the chip.
3: protrusions caused by cutting chips or retentate were observed at the corners of the chip, and the protrusions contaminated more than 50% of the corners of the chip.
Evaluation (3): contamination of the chip side
0: no cutting chips or retentate was observed on the chip side.
1: cutting chips or retentate were observed on the chip side, which contaminated more than 1% and less than 20% of the chip side.
2: cutting chips or retentate were observed on the chip side, which contaminated more than 20% and less than 50% of the chip side.
3: cutting chips or retentate were observed on the chip side, and the cutting chips or retentate contaminated more than 50% of the chip side.
According to examples 1 to 5, it was found that when the curable resin film having an elongation at break of 85% or less at 70 ℃ after curing was used for the protective film formation of a semiconductor chip, a semiconductor chip having excellent processing quality with less deformation of the cut surface and less adhesion of cutting chips and retentate could be obtained.

Claims (9)

1. A curable resin film for forming a protective film on both a bump formation surface and a side surface of a semiconductor chip having the bump formation surface,
wherein the elongation at break of the curable resin film after curing at 70 ℃ is 85% or less.
2. The curable resin film according to claim 1, wherein,
the product of elongation at break at 70 ℃ after curing of the curable resin film is 1000 or less.
3. The curable resin film according to claim 1 or 2, which has a thickness of 30 μm or more.
4. A composite sheet having a laminated structure obtained by laminating the curable resin film according to any one of claims 1 to 3 and a release sheet.
5. The composite sheet according to claim 4, wherein,
the release sheet has a base material and a release layer that faces the curable resin film.
6. The composite sheet of claim 5 further having an intermediate layer between the substrate and the release layer.
7. The composite sheet according to claim 5 or 6, wherein,
the release layer is a layer formed from a composition comprising an ethylene vinyl acetate copolymer.
8. A method for manufacturing a semiconductor chip, comprising the following steps (S1) to (S4) in this order,
step (S1): a step of preparing a wafer for semiconductor chip production, in which grooves as lines to divide are formed in a bump formation surface of a semiconductor wafer having the bump formation surface of a bump so as not to reach a back surface;
step (S2): a step of pressing and adhering the curable resin film according to any one of claims 1 to 3 to the bump formation surface of the semiconductor chip manufacturing wafer, coating the bump formation surface of the semiconductor chip manufacturing wafer with the curable resin film, and embedding the curable resin film in the groove portion formed in the semiconductor chip manufacturing wafer;
Step (S3): a step of curing the curable resin film to obtain a wafer for manufacturing a semiconductor chip having a cured resin film;
step (S4): a step of singulating the wafer for manufacturing semiconductor chips with the cured resin film along the predetermined dividing lines to obtain semiconductor chips having at least the bump formation surfaces and the side surfaces covered with the cured resin film,
and, after the step (S2) and before the step (S3), after the step (S3) and before the step (S4), or in the step (S4), the method comprises the following step (S-BG),
step (S-BG): and grinding the back surface of the wafer for manufacturing the semiconductor chip.
9. A semiconductor chip having the cured resin film obtained by curing the curable resin film according to any one of claims 1 to 3 on both the bump formation surface and the side surface of the semiconductor chip having the bump formation surface.
CN202310085287.1A 2022-01-28 2023-01-19 Curable resin film, composite sheet, semiconductor chip, and method for manufacturing semiconductor chip Pending CN116515237A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-012254 2022-01-28
JP2022012254 2022-01-28

Publications (1)

Publication Number Publication Date
CN116515237A true CN116515237A (en) 2023-08-01

Family

ID=87394650

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310085287.1A Pending CN116515237A (en) 2022-01-28 2023-01-19 Curable resin film, composite sheet, semiconductor chip, and method for manufacturing semiconductor chip

Country Status (4)

Country Link
JP (1) JP2023110879A (en)
KR (1) KR20230116659A (en)
CN (1) CN116515237A (en)
TW (1) TW202342600A (en)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5830250B2 (en) 2011-02-15 2015-12-09 日東電工株式会社 Manufacturing method of semiconductor device
JP2015092594A (en) 2014-12-10 2015-05-14 日東電工株式会社 Protection layer formation film

Also Published As

Publication number Publication date
KR20230116659A (en) 2023-08-04
JP2023110879A (en) 2023-08-09
TW202342600A (en) 2023-11-01

Similar Documents

Publication Publication Date Title
TWI489588B (en) A substrate film for a cutting sheet, and a cutting sheet
US9434865B2 (en) Adhesive composition, an adhesive sheet and a production method of a semiconductor device
JP6437431B2 (en) Manufacturing method of semiconductor chip
CN110461973B (en) Film-like adhesive composite sheet and method for manufacturing semiconductor device
KR20190030667A (en) Dicing·die bonding sheet
CN107001875B (en) Film-like adhesive composite sheet and method for manufacturing semiconductor device
KR20200108785A (en) Dicing tape with adhesive film
CN111466015B (en) Die bonding film, dicing die bonding sheet, and method for manufacturing semiconductor chip
WO2013015012A1 (en) Base material film for semiconductor processing sheet, semiconductor processing sheet, and method for manufacturing semiconductor device
CN114730707A (en) Sheet for manufacturing semiconductor device and method for manufacturing semiconductor chip with film-like adhesive
JP2022125110A (en) Die bonding sheet and method for manufacturing semiconductor chip with film type adhesive
CN116515237A (en) Curable resin film, composite sheet, semiconductor chip, and method for manufacturing semiconductor chip
CN116515238A (en) Curable resin film, composite sheet, semiconductor chip, and method for manufacturing semiconductor chip
WO2023145589A1 (en) Thermosetting resin film, composite sheet, semiconductor chip, and production method for semiconductor chip
CN114930504A (en) Curable resin film, composite sheet, and method for producing semiconductor chip
TWI838470B (en) Semiconductor back side bonding film and wafer-cutting tape integrated semiconductor back side bonding film
CN113508167B (en) Method for manufacturing die-attach sheet and semiconductor chip with film-like adhesive
TW202348757A (en) Protective film-forming film, composite sheet for forming protective film, method of manufacturing semiconductor device, and use of protective film-forming film providing a protective film-forming composite sheet including a support sheet and the protective film-forming film provided on one surface of the support sheet
CN112839767A (en) Method for manufacturing workpiece with first protective film
TW202142647A (en) Film-like adhesive and film-like adhesive composite sheet having a fracture strength is 30 MPa or less and a percentage elongation at break is more than 11%
CN114902377A (en) Method for manufacturing semiconductor chip

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication