CN115404015A - Adhesive film for wafer processing - Google Patents

Adhesive film for wafer processing Download PDF

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Publication number
CN115404015A
CN115404015A CN202210580217.9A CN202210580217A CN115404015A CN 115404015 A CN115404015 A CN 115404015A CN 202210580217 A CN202210580217 A CN 202210580217A CN 115404015 A CN115404015 A CN 115404015A
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China
Prior art keywords
adhesive
layer
adhesive film
wafer processing
substrate layer
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CN202210580217.9A
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Chinese (zh)
Inventor
郑喆
高乾英
崔裁原
金尚信
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Innox Corp
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Innox Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • 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
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding

Abstract

The invention provides an adhesive film for wafer processing, which comprises: a multilayer substrate comprising an upper substrate layer and a lower substrate layer; a first adhesive layer disposed on the upper base material layer; and a second adhesive layer disposed between the upper substrate layer and the lower substrate layer, the second adhesive layer being made of a second adhesive composition including an adhesive resin and core-shell nanoparticles.

Description

Adhesive film for wafer processing
Technical Field
The present invention relates to an adhesive film for wafer processing used for wafer processing such as thin film back grinding of a wafer. More particularly, the present invention relates to an adhesive film for wafer processing having an excellent surface protection effect (cushion effect) of a wafer during wafer polishing.
Background
Recently, with the development of technology, there is a growing demand for miniaturization and thinning of semiconductor chips.
As a representative example of thinning of the chip, there is a method of reducing the thickness by polishing the back surface of the wafer on which the chip is formed.
Recently, a thinned chip is obtained by a back side Grinding (DBG) method, and a diced chip is obtained from a wafer by forming a groove on a front surface of the wafer by a Dicing blade and then Grinding a back surface of the wafer. When the wafer back-grinding method is used, the back-grinding of the wafer and the dicing of the wafer are performed simultaneously, and therefore, a thin semiconductor chip can be efficiently manufactured.
In general, when back-grinding a wafer, the back-grinding of the wafer is performed in a state where an adhesive film is attached to the front surface of the wafer in order to maintain the semiconductor chip. Such an adhesive film includes an adhesive layer for bonding the substrate and the wafer surface, and a cushion layer or a vibration damping layer having a cushion effect, for example, urethane acrylate, may be formed on the back surface of the substrate.
The lower the modulus (modulus) of such a buffer layer, the more excellent the buffer effect, and thus the surface of the wafer can be effectively protected. However, there may be a problem that, in the case of a buffer layer having a low modulus, the buffer layer flows at a high temperature or becomes non-uniform in thickness due to an increase in temperature when a back grinding process is performed.
Disclosure of Invention
Technical problem
An object of the present invention is to provide an adhesive film for wafer processing, which can protect the surface of a wafer by an excellent cushion effect during back grinding of the wafer, and can improve the fluidity control and thickness uniformity at high temperatures.
Objects of the present invention are not limited to the above-mentioned objects, and other objects and advantages of the present invention, which are not mentioned, can be understood by the following description and more clearly understood by embodiments of the present invention. Also, it is apparent that the objects and advantages of the present invention can be achieved by the means and combinations thereof as expressed in the claims.
Technical scheme
In order to solve the above-mentioned technical problem, the adhesive film for wafer processing of the present invention may include: a multilayer substrate comprising an upper substrate layer and a lower substrate layer; a first adhesive layer disposed on the upper base material layer; and a second adhesive layer disposed between the upper substrate layer and the lower substrate layer, wherein the second adhesive layer is made of a second adhesive composition, and the second adhesive composition includes an adhesive resin and core-shell nanoparticles.
The average particle diameter of the core-shell nanoparticles may be 5nm to 400nm.
The core of the core-shell nanoparticle may be polyalkyl (meth) acrylate having a glass transition temperature of-50 to 40 ℃, and the shell of the core-shell nanoparticle may be polyalkyl (meth) acrylate having a glass transition temperature of 50 to 150 ℃.
The core-shell nanoparticles may be included in an amount of 0.1 to 20 parts by weight, based on 100 parts by weight of the binder resin of the second binder composition.
The second adhesive layer may have a modulus (modulus) of 0.05 to 2MPa at a temperature of 60 to 90 ℃.
The recovery force (recovery force) of the adhesive film may be 55% to 90% as measured according to the following formula 1. The method for measuring the recovery force by the formula 1 will be specifically described below.
Formula 1: restoring force (%) = (1- (X) f /X 0 ))×100
In the above formula 1, X 0 Is a thickness 1/2 times as large as the initial thickness of the adhesive film, X f Is at X 0 The thickness of the adhesive film when no force is applied to the adhesive film when the adhesive film is recovered after 10 seconds of holding.
The modulus of the lower substrate layer and the upper substrate layer may be 1000MPa or more at a temperature of 23 ℃.
The lower substrate layer and the upper substrate layer may each include one or more selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, wholly aromatic polyester, polyimide, polyamide, polycarbonate, polyacetal, modified polyphenylene ether, polyphenylene sulfide, polysulfone, polyether ketone, and biaxially oriented polypropylene.
The adhesive resin of the second adhesive layer may contain a thermosetting acrylic adhesive.
A primer layer may be additionally formed on at least one of the upper surface of the upper substrate layer, the lower surface of the upper substrate layer, and the upper surface of the lower substrate layer.
ADVANTAGEOUS EFFECTS OF INVENTION
The adhesive film for wafer processing of the present invention can realize an excellent buffering effect (restoring force) of a wafer surface and improve flow control and thickness uniformity at high temperatures when performing back grinding processing of a wafer by including the second adhesive layer in which core-shell nanoparticles are included.
The effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned can be clearly understood by those skilled in the art from the following description.
In addition to the above-described effects, the specific effects of the present invention will be described together in the following description of specific embodiments of the present invention.
Drawings
Fig. 1 is a cross-sectional view schematically showing an adhesive film for wafer processing according to an embodiment of the present invention.
Fig. 2 is a cross-sectional view schematically showing an adhesive film for wafer processing according to another embodiment of the present invention.
Description of the reference numerals:
110: a substrate;
111: a lower substrate layer;
112: an upper substrate layer;
113: a primer layer;
115: a second adhesive layer;
120: a first adhesive layer.
Detailed Description
The above objects, features and advantages will be described in detail below with reference to the accompanying drawings so that those skilled in the art can easily implement the technical idea of the present invention. In describing the present invention, a detailed description thereof will be omitted when it is judged that a detailed description of a known technology related to the present invention may make the gist of the present invention unclear. Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the drawings, the same reference numerals denote the same or similar structural elements.
In the present specification, the term "any structure is disposed on" an upper portion (or a lower portion) "of a structural element or" upper (or lower) "of a structural element may mean that any structure is disposed not only in contact with an upper surface (or a lower surface) of the structural element but also that another structure may be provided between the structural element and any structure disposed on (or under) the structural element.
In this specification, the singular expressions used include plural expressions unless the context clearly indicates otherwise. In the present application, the terms "constituting" or "including" should not be construed as necessarily including all of the structural elements described in the specification, as they may not include some of the structural elements, or as may include additional structural elements.
In the present description, terms such as "one side", "the other side" and "both sides" are used only to distinguish one component from another component, and the component is not limited to the above terms.
In the present invention, the wafer processing may include a wafer back grinding (back grinding) process, a dicing process, a pick-up process of diced semiconductor chips, and the like.
Hereinafter, in describing the present invention, detailed descriptions about known technologies that may unnecessarily obscure the gist of the present invention will be omitted.
The adhesive film for wafer processing of the present invention will be described in detail below.
The adhesive film for wafer processing of the present invention may comprise: a multilayer substrate comprising an upper substrate layer and a lower substrate layer; a first adhesive layer disposed on the upper base material layer; and a second adhesive layer disposed between the upper substrate layer and the lower substrate layer, the second adhesive layer being made of a second adhesive composition, the second adhesive composition including an adhesive resin and core-shell nanoparticles.
Fig. 1 is a cross-sectional view schematically showing an adhesive film for wafer processing according to an embodiment of the present invention. Referring to fig. 1, the adhesive film for wafer processing according to the present invention includes: a multi-layer substrate 110; a first adhesive layer 120 disposed on the upper base material layer 112 of the multilayer base material; and a second adhesive layer 115 disposed between the upper substrate layer 112 and the lower substrate layer 111.
Multilayer substrate
The multilayer substrate 110 includes a lower substrate layer 111, an upper substrate layer 112, and a second adhesive layer 115. First adhesive layer 120 is disposed on upper base material layer 112, and second adhesive layer 115 is disposed between lower base material layer 111 and upper base material layer 112. In the adhesive film for wafer processing of the present invention, the multilayer substrate has a sandwich structure in which the second adhesive layer 115 is disposed between the lower substrate layer 111 and the upper substrate layer 112.
The lower substrate layer 111 and the upper substrate layer 112 may be made of a high modulus material. More specifically, the lower base material layer 111 and the upper base material layer 112 may have a modulus of 1000MPa or more, for example, 1200MPa or more, 1500MPa or more, 2000MPa or more, and 3000MPa or more, based on the measured value at a temperature of 23 ℃. The present invention is characterized in that the upper substrate layer 112 and the lower substrate layer 111 are made of a material having a high modulus at the side to which the wafer is bonded.
When the modulus of the upper base material layer 112 and the lower base material layer 111 is relatively low, in other words, less than 1000MPa, the supporting force of the wafer or the diced semiconductor chips may be reduced, which may cause the semiconductor chips to collide in the back grinding step.
The lower substrate layer 111 and the upper substrate layer 112 may each include one or more selected from the group consisting of polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and wholly aromatic polyesters, polyimide (PI), polyamide (PA), polycarbonate (PC), polyacetal, modified polyphenylene ether, polyphenylene sulfide, polysulfone, polyether ketone, and biaxially Oriented polypropylene (Oriented Poly-propylene).
Preferably, the lower substrate layer 111 and the upper substrate layer 112 may be made of the same material. For example, the lower substrate layer 111 and the upper substrate layer 112 may be made of polyethylene terephthalate (PET).
Although the lower substrate layer 111 and the upper substrate layer 112 may have the same thickness, they are not limited thereto. The lower substrate layer 111 and the upper substrate layer 112 may have a thickness of about 10 to 150 μm, respectively. On the other hand, in the present invention, although the lower base material layer 111 and the upper base material layer 112 have a high modulus, when the thicknesses of the lower base material layer 111 and the upper base material layer 112 are relatively thick, particularly, if the thickness of the upper base material layer 112 is too thick, it is difficult to withstand an impact generated during a wafer processing such as back grinding. Therefore, the thickness of the lower base material layer 111 and the upper base material layer 112 is preferably 150 μm or less.
On the other hand, lower substrate layer 111 and/or upper substrate layer 112 may contain small amounts of various additives, for example, coupling agents, plasticizers, antistatic agents, antioxidants, and the like.
First adhesive layer
The first adhesive layer 120 shown in fig. 1 is a portion to be adhered to the wafer.
The first adhesive layer 120 is not particularly limited as long as it has proper adhesiveness at room temperature, and various adhesives such as a known Ultraviolet (UV) adhesive may be applied.
The thickness of the first adhesive layer 120 is not particularly limited, and may be, for example, 10 μm to 100 μm.
Fig. 2 is a cross-sectional view schematically showing an adhesive film for wafer processing according to still another embodiment of the present invention.
Referring to fig. 2, a primer layer 113 may be additionally included on the upper surface of the upper base material layer 112 of the multi-layered substrate. Such a primer layer 113 may be used to improve adhesion between the first adhesive layer 120 and the multilayer substrate 110.
The primer layer 113 is formed on the upper surface of the upper base material layer 112, that is, a separate layer may be formed on the side on which the first adhesive layer 120 is formed. As another example, the primer layer 113 may be formed by modifying the upper surface of the upper base material layer 112.
Although fig. 2 shows the primer layer 113 formed on the upper surface of the upper base material layer 112 as an example, the present invention is not limited to this, and the primer layer may be formed on the lower surface of the upper base material layer 112 or on the upper surface of the lower base material layer 111.
Although not shown in fig. 2, the present invention may further include a release film disposed on the upper surface of the first adhesive layer and bonded thereto by the adhesive layer. One side of the release film can be subjected to release treatment. The release treatment is not limited as long as it is a material generally used in the release treatment in this field, and for example, it is preferable to perform the release treatment using silicon.
Second adhesive layer
In the present invention, the second adhesive layer 115 is an adhesive layer disposed between the upper base material layer 112 and the lower base material layer 111, and can function as a cushion layer or a vibration damping layer having a high cushion effect for protecting the wafer surface during wafer processing.
Preferably, the second adhesive layer of the present invention is made of a second adhesive composition comprising an adhesive resin and core-shell nanoparticles. The second adhesive layer may be manufactured by thermally curing the above-described second adhesive composition.
The binder resin of the above-described second binder composition may include a thermosetting acrylic binder resin, and the second binder composition may include a heat curing agent in addition to the binder resin.
For example, the thermosetting acrylic binder resin may be a methyl acrylate compound. Examples of the methyl acrylate compound that can be used for the thermosetting acrylic adhesive include, but are not limited to, (meth) acrylic acid esters, (meth) acrylic acid alkyl esters such as (meth) acrylic acid alkyl esters having an alkyl group of 4 or more carbon atoms, and non-urethane polyfunctional (meth) acrylic acid esters.
Examples of the curing agent that can be used for the thermosetting acrylic adhesive include, but are not limited to, isocyanate-based crosslinking agents, carbodiimide-based crosslinking agents, oxazoline-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, and peroxides. The content of the curing agent may be 2 parts by weight or less with respect to 100 parts by weight of the binder resin of the second binder composition, but is not limited thereto.
The lower the modulus of the second adhesive layer as the buffer layer is, the more advantageous the buffer effect is, but when the modulus is too low, there is a possibility that the buffer layer flows at a high temperature or becomes uneven in thickness due to a temperature increase at the time of performing the back grinding process.
Accordingly, the present inventors have found that the above-mentioned problems can be solved by including core-shell structured nanoparticles in the second adhesive layer in order to control the fluidity of the second adhesive layer due to heat generated during the wafer back-grinding process.
The average particle diameter of the core-shell structured nanoparticle is preferably 5nm to 400nm, more preferably 100nm to 300nm. If the average particle diameter of the nanoparticles is less than 5nm, dispersion unevenness may occur due to aggregation caused by inter-particle static electricity, and if the average particle diameter of the nanoparticles is more than 400nm, a problem may occur in that the surface of the coating layer becomes uneven and the thickness uniformity is not good.
The core of the above core-shell nanoparticle plays a role of maintaining modulus at high temperature by forming a cross-linked structure, and thus, is preferably made of a material having a low glass transition temperature.
The glass transition temperature of the core of the above core-shell nanoparticles may be-50 ℃ to 40 ℃, more preferably, -30 ℃ to 30 ℃, and most preferably, -30 ℃ to 20 ℃. In the above glass transition temperature range, the cushioning effect required in the process temperature range (40 ℃ C. To 90 ℃ C.) can be achieved against the impact generated during back grinding.
If the glass transition temperature of the core is higher than 40 ℃, the absorption capability of the impact generated in the temperature range of the processing process is limited, and thus the chip crack (chip crack) may be caused, and if the glass transition temperature of the core is lower than-50 ℃, the particle shape may be easily deformed by the pressure during the processing process, and a problem may occur in the impact absorption function.
For example, the core may comprise one or more polyalkyl (meth) acrylates having a glass transition temperature in the range of-50 ℃ to 40 ℃. Preferably, the core may include one or more of polymethyl acrylate, polyethyl acrylate, polycyclohexyl acrylate, benzyl acrylate, isopropyl acrylate, polybutyl methacrylate, polyhexamethyl methacrylate, polymethyl cyanoacrylate, and poly-2-cyanoethyl methacrylate, but is not limited thereto. More preferably, the core may include one or more of polymethyl acrylate and polybutyl methacrylate.
Preferably, the shell of the core-shell nanoparticle functions to form a hard structure, and is made of a material having a high glass transition temperature in order to secure dispersibility in the binder layer.
The glass transition temperature of the shell of the above core-shell nanoparticles may be 50 ℃ to 150 ℃, more preferably 60 ℃ to 130 ℃, and most preferably 80 ℃ to 130 ℃.
When the glass transition temperature of the shell is less than 50 ℃, aggregation (aggregation) may occur due to a decrease in particle dispersibility, or the organic particles may be deformed due to heat generated during the processing step, thereby decreasing the recovery performance of the adhesive film under impact. If the glass transition temperature of the shell is more than 150 ℃, the buffering effect may be deteriorated due to the increased hardness of the particles.
For example, the shell may comprise a polyalkyl (meth) acrylate having a glass transition temperature of 50 ℃ to 150 ℃. Preferably, the shell may include one or more of Polymethylmethacrylate (PMMA), polyethylmethacrylate, polypropylmethacrylate, polybutylmethacrylate, polyisopropylmethacrylate, polyisobutylmethacrylate, and polycyclohexylmethacrylate, but is not limited thereto. More preferably, the shell may comprise polymethylmethacrylate.
The shell may be included by 1 to 70 parts by weight, preferably 5 to 60 parts by weight, and more preferably 10 to 50 parts by weight, with respect to 100 parts by weight of the core-shell nanoparticle. If the content of the shell in the core-shell nanoparticles is less than 1 part by weight, the core cannot be sufficiently surrounded, and the wafer surface protection effect in the back grinding process is reduced, whereas if it is more than 70 parts by weight, the hard shell portion is too large, and the buffer effect is reduced, and the restoring force of the adhesive film cannot be satisfactorily maintained. Therefore, the balance between the cushioning effect and the modulus can be maintained only when the shell satisfies the range of 1 to 70 parts by weight based on the core-shell nanoparticles.
The core-shell nanoparticles may be included in an amount of 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, and most preferably 2 to 8 parts by weight, based on 100 parts by weight of the binder resin of the second binder composition. If the content of the core-shell nanoparticles is less than 0.1 parts by weight, the buffering effect of the nanoparticles may be insignificant, and if it exceeds 20 parts by weight, non-uniform aggregation may occur due to a decrease in adhesive force or a deterioration in dispersibility of the particles, and the buffering effect may be halved.
Preferably, the modulus of the second adhesive layer in the temperature range of 60 ℃ to 90 ℃ is 0.05MPa to 2MPa, more preferably 0.05MPa to 1MPa.
Preferably, the modulus of the second adhesive layer is 2MPa or less, since the use of a low-modulus material is advantageous in further improving the cushioning effect characteristics. However, if the modulus is too low, the fluidity of the adhesive layer increases, and therefore, there is a possibility that the thickness becomes uneven due to the pressure applied in the back grinding step of the wafer, and therefore, it is preferable that the modulus of the second adhesive layer at high temperature be 0.05MPa or more.
Preferably, the adhesive film of the present invention has a restoring force of 55 to 90%, more preferably 65 to 90%, most preferably 70 to 90%, measured based on the following formula 1.
Formula 1: restoring force (%) = (1- (X) f /X 0 ))×100
In the above formula 1, X0 is a thickness 1/2 times the original thickness of the adhesive film, and X f Is at X 0 The thickness of the adhesive film when no force is applied to the adhesive film when the adhesive film is restored after 10 seconds of holding.
According to the present invention, the adhesive film having a restoring force of 55% to 90% does not deform even under heat and pressure generated in the wafer back grinding process, and thus can maintain stable thickness uniformity of the wafer chips. If the restoring force is less than 55%, the surface protection effect is insufficient when the wafer processing step is performed, and if the restoring force is greater than 90%, the cushion effect is reduced, and the impact generated when the back grinding step is performed is transmitted to the wafer, and thus the wafer may be broken.
In the present invention, the restoring force of the adhesive film is intended to measure the restoring force of the film including the adhesive layer, and is measured using a physical property tester (ta.xt _ Plus), and the specific measurement method is as follows.
Measurement method
Test pieces bonded in the order of polyethylene terephthalate (PET) film (50 μm)/adhesive film (length. Times. Width: 20 mm. Times.20 mm, thickness: 60 μm)/polyethylene terephthalate film (50 μm) were fixed on a plate, and then pressed at a high temperature (60 ℃) using a rectangular probe (probe) at a speed of 300mm/min to a thickness that becomes 1/2 times the original thickness of the adhesive film, i.e., X 0 (unit: μm), holding for 10 seconds, recovering at the same speed (300 mm/min) as the pressing speed, and pressing the adhesive film with a force of 0kPa to obtain a thickness X f (unit: μm), the restoring force (%) was calculated by the above formula 1.
Hereinafter, the structure and operation of the present invention will be described in more detail by way of preferred embodiments of the present invention. However, this is a preferred illustration of the invention and should not be construed as limiting the invention in any way.
Preparation example
Preparation example 1: composition for Forming second adhesive layer ("M1")
A mixture obtained by mixing 42 parts by weight of butyl acrylate, 10 parts by weight of ethylhexyl acrylate, 30 parts by weight of methyl acrylate, 5 parts by weight of 2-hydroxyethyl acrylate, 13 parts by weight of acrylic acid, 0.05 parts by weight of azobisisobutyronitrile, and 100 parts by weight of ethyl acetate was polymerized at a temperature of 60 ℃ for 6 hours under a nitrogen atmosphere, to obtain acrylic resin polymerization liquid a having a weight average molecular weight of 80 ten thousand.
An isocyanate-based curing agent (trade name "Coronate C", manufactured by japan polyurethane industries, ltd.) was added in an amount of 2 parts by weight based on 100 parts by weight of the acrylic resin polymerization liquid a to obtain a second pressure-sensitive adhesive layer-forming composition (denoted by "M1").
Preparation example 2: composition for Forming second adhesive layer ("M2")
A mixture obtained by mixing 20 parts by weight of butyl acrylate, 10 parts by weight of ethylhexyl acrylate, 55 parts by weight of methyl acrylate, 7 parts by weight of 2-hydroxyethyl acrylate, 8 parts by weight of acrylic acid, 0.05 parts by weight of azobisisobutyronitrile, and 100 parts by weight of ethyl acetate was polymerized at a temperature of 60 ℃ for 6 hours under a nitrogen atmosphere, to obtain acrylic resin polymerization liquid B having a weight average molecular weight of 60 ten thousand.
An isocyanate-based curing agent (trade name "Coronate C", manufactured by japan polyurethane industries, ltd.) was added in an amount of 3 parts by weight based on 100 parts by weight of the acrylic resin polymerization liquid B to obtain a second pressure-sensitive adhesive layer-forming composition (denoted by "M2").
Preparation example 3: composition for Forming first adhesive layer ("A1")
A reactor equipped with a cooling device in such a manner as to allow nitrogen to circulate and facilitate temperature regulation was charged with a monomer mixture consisting of 27g of Butyl Acrylate (BA), 48g of Methyl Acrylate (MA) and 25g of hydroxyethyl acrylate (HEA).
Next, 100 parts by weight of ethyl acetate (EAc) as a solvent was put into 100 parts by weight of the monomer mixture, nitrogen was injected into the reactor for removing oxygen, and the mixture was sufficiently mixed at a temperature of 30 ℃ for 30 minutes or more. Next, the temperature was maintained at 50 ℃, and after 0.1 part by weight of azobisisobutyronitrile as a reaction initiator was charged and the reaction was initiated, the first reactant was prepared by polymerization for 24 hours.
24.6 parts by weight of methacryloyloxyethyl isocyanate (MOI) and a catalyst (DBTDL: dibutyl tin dilaurate) at a weight ratio of 1% to the MOI were added to the first reactant, and the mixture was reacted at 40 ℃ for 24 hours to obtain an acrylic polymer C having a weight average molecular weight of 50 ten thousand.
To 100 parts by weight of the acrylic polymer C, 0.1 part by weight of a photoinitiator (Irgacure) 184 (trade name, manufactured by BASF) was added as a photopolymerization initiator, and 2 parts by weight of an isocyanate-based curing agent (trade name "Coronate C", manufactured by japan polyurethane industries, ltd.) was added to obtain a first adhesive layer forming composition (denoted as "A1").
Preparation example 4: core-shell nanoparticles ("b 1")
The core is formed of polymethyl acrylate (PMA, tg:10 ℃) and the shell is formed of polymethyl methacrylate (PMMA, tg:105 ℃), thereby constituting a core-shell structure in which the shell has an average particle diameter of 230nm at 40 parts by weight with respect to 100 parts by weight of the core-shell nanoparticles.
Preparation example 5: core-shell nanoparticles ("b 2")
The core is formed of polymethyl acrylate (PMA) and the shell is formed of polymethyl methacrylate (PMMA), thereby constituting a core-shell structure in which the shell is 30 parts by weight and the average particle diameter is 130nm, with respect to 100 parts by weight of the core-shell nanoparticles.
Examples
Example 1
The first adhesive layer-forming composition ("A1") in production example 3 was applied on a release-treated polyethylene terephthalate (PET) film (thickness of 50 μm) so that the thickness of the first adhesive layer became 20 μm, and then a film having a first adhesive layer with a total thickness of 120 μm was produced by bonding a polyethylene terephthalate substrate film (thickness of 50 μm) on which a primer layer was formed.
Next, the core-shell nanoparticles B1 in production example 4 were added and mixed to the second binder layer forming composition ("M2") in production example 2 in such a manner that the ratio between the acrylic resin polymerization liquid B and the core-shell nanoparticles B1 in production example 4 reached 100 parts by weight to 4 parts by weight, and then coated on a polyethylene terephthalate film (thickness of 20 μ M) in a thickness of 20 μ M, thereby producing a film having a second binder layer with a total thickness of 40 μ M.
The film having the first adhesive layer and the film having the second adhesive layer were joined to prepare a composite film having a total thickness of 160 μm, and the adhesive film for wafer processing was finally prepared by using a protective sheet.
Example 2
Preparation was performed in the same manner as in example 1, except that the second adhesive layer forming adhesive composition ("M2") in preparation example 2 was replaced with the second adhesive layer forming adhesive composition ("M1") in preparation example 1 as a second adhesive layer and "b2" in preparation example 5 was replaced with "b1" in preparation example 4 as core-shell nanoparticles.
Example 3
Preparation was performed in the same manner as in example 1, except that "M2" was used and coating was performed on a polyethylene terephthalate film (thickness: 20 μ M) in a thickness of 50 μ M to form a second adhesive layer having a total thickness of 70 μ M.
Example 4
Preparation was carried out in the same manner as in example 2, except that "M1" was used and coating was carried out on a polyethylene terephthalate film (thickness of 20 μ M) at a thickness of 50 μ M to form a second binder layer having a total thickness of 70 μ M and the content of "b2" in preparation example 5 as core-shell nanoparticles was made to 2 parts by weight.
Example 5
Preparation was performed in the same manner as in example 1, except that "M2" was used and coating was performed on a polyethylene terephthalate film (thickness of 20 μ M) at a thickness of 80 μ M to form a second adhesive layer having a total thickness of 100 μ M, and 8 parts by weight of "b2" in preparation example 5 was used instead of "b1" in preparation example 4 as core-shell nanoparticles.
Example 6
Preparation was carried out in the same manner as in example 2, except that "M1" was used and coating was carried out on a polyethylene terephthalate film (thickness: 20 μ M) at a thickness of 80 μ M to form a second binder layer having a total thickness of 100 μ M, and 8 parts by weight of the core-shell nanoparticles "b2" in preparation example 5 were used.
Comparative example 1
Preparation was performed in the same manner as in example 4, except that the core-shell nanoparticles were not included in the second binder layer.
Comparative example 2
Preparation was performed in the same manner as in example 3, except that "b1" in preparation example 4 was used as the core-shell nanoparticles instead of "b2" in preparation example 5 and the content thereof was made to 25 parts by weight.
Examples of the experiments
Experimental example 1: modulus (60 ℃ C. And 90 ℃ C.) of adhesive film
The modulus under a temperature environment of from-20 ℃ to 120 ℃ was measured on a sample having a size of 8mm × 1mm in thickness obtained by laminating a single-layer adhesive layer formed of a solution of the second adhesive layer forming composition used in examples and comparative examples under a condition of 1Hz by using a Rheometer (Rheometer, TA instruments, ARES-G2) as a modulus measuring apparatus, and the moduli at the temperatures of 60 ℃ and 90 ℃ were recorded and are described in table 1.
Experimental example 2: restoring force
The restoring force of the adhesive film was measured by using a physical property tester (ta.xt _ Plus) to measure the restoring force of the film including the adhesive layer, calculated based on the following formula 1, and the specific measurement method was as follows.
Formula 1: restoring force (%) = (1- (X) f /X 0 ))×100
Measurement method
Test pieces bonded in the order of polyethylene terephthalate (PET) film (50 μm)/adhesive film (length. Times. Width: 20 mm. Times.20 mm, thickness: 60 μm)/polyethylene terephthalate film (50 μm) were fixed on a plate, and then pressed at a high temperature (60 ℃) using a rectangular probe (probe) at a speed of 300mm/min to a thickness that becomes 1/2 times the original thickness of the adhesive film, i.e., X 0 (unit: μm), holding for 10 seconds, recovering at the same speed (300 mm/min) as the pressing speed, and pressing the adhesive film with a force of 0kPa to obtain a thickness X f (unit: μm), the restoring force (%) was calculated by the above formula 1.
The restoring force of the adhesive films in examples 1 to 6 and comparative examples 1 to 2 was measured according to the above formula 1 and the measurement method, and is shown in table 1.
Experimental example 3: wafer grinding test (thickness uniformity)
The adhesive films of examples 1 to 6 and comparative examples 1 to 2 were attached to the surface of a semiconductor circuit, and then 725 μm wafers were back-polished to a thickness of 100 μm. By irradiating UV A300 mJ/cm 2 The adhesive film was removed and then the average thickness uniformity at 10 points in the wafer after grinding was compared. If the average value of the thickness variation at each point is 4 μm or less, the value is evaluated as "O" (good), and if the average value is 6 μm or more, the value is evaluated as "X" (bad).
TABLE 1
Figure BDA0003662074370000141
As shown in table 1 above, examples 1 to 6 including core-shell nanoparticles have superior restoring force and thickness uniformity compared to comparative example 1. In comparative example 2, the modulus value of the second adhesive layer was greater than 2MPa, the restoring force was greater than 90%, the cushioning property was insufficient, and it was difficult to measure the thickness uniformity.
While the present invention has been described above with reference to the accompanying drawings, it is to be understood that the present invention is not limited to the embodiments and the drawings disclosed herein, and that various modifications can be made by those skilled in the art within the scope of the technical spirit of the present invention. Further, it should be understood that the operational effects of the configurations of the present invention, which are not explicitly described in the description of the embodiments of the present invention, include effects that can be predicted by the corresponding configurations.

Claims (11)

1. An adhesive film for wafer processing, characterized in that,
the method comprises the following steps:
a multilayer substrate comprising an upper substrate layer and a lower substrate layer;
a first adhesive layer disposed on the upper base material layer; and
a second adhesive layer disposed between the upper base material layer and the lower base material layer,
the second adhesive layer is made of a second adhesive composition, and the second adhesive composition includes an adhesive resin and core-shell nanoparticles.
2. The bonding film for wafer processing according to claim 1, wherein the core-shell nanoparticles have an average particle diameter of 5nm to 400nm.
3. The adhesive film for wafer processing according to claim 1,
the core of the core-shell nano particle is polyalkyl (methyl) acrylate with the glass transition temperature of-50 to 40 ℃,
the shell of the core-shell nanoparticle is polyalkyl (meth) acrylate with a glass transition temperature of 50 ℃ to 150 ℃.
4. The adhesive film for wafer processing according to claim 1, wherein the core-shell nanoparticles are contained in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the adhesive resin of the second adhesive composition.
5. The adhesive film for wafer processing as claimed in claim 1, wherein the modulus of the second adhesive layer at a temperature ranging from 60 ℃ to 90 ℃ is 0.05MPa to 2MPa.
6. The adhesive film for wafer processing according to claim 1,
the adhesive film has a restoring force of 55 to 90% as measured by the following formula 1,
formula 1: restoring force (%) = (1- (X) f /X 0 ))×100
In the above formula 1, X 0 A thickness 1/2 times the original thickness of the adhesive film, X f Is at X 0 The thickness of the adhesive film when no force is applied to the adhesive film when the adhesive film is recovered after 10 seconds of holding.
7. The adhesive film for wafer processing according to claim 1, wherein the modulus of the lower substrate layer and the upper substrate layer is 1000MPa or more at a temperature of 23 ℃.
8. The adhesive film for wafer processing according to claim 1, wherein each of the lower substrate layer and the upper substrate layer comprises at least one selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, wholly aromatic polyester, polyimide, polyamide, polycarbonate, polyacetal, modified polyphenylene ether, polyphenylene sulfide, polysulfone, polyether ketone, and biaxially oriented polypropylene.
9. The adhesive film for wafer processing as claimed in claim 8, wherein the lower substrate layer and the upper substrate layer are made of polyethylene terephthalate.
10. The adhesive film for wafer processing as set forth in claim 1, wherein the adhesive resin of the second adhesive layer comprises a thermosetting acrylic adhesive resin.
11. The adhesive film for wafer processing according to claim 1, wherein a primer layer is additionally formed on at least one of the upper surface of the upper substrate layer, the lower surface of the upper substrate layer, and the upper surface of the lower substrate layer.
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JP2012054518A (en) * 2010-09-03 2012-03-15 Sekisui Chem Co Ltd Adhesive for bonding semiconductor, adhesive film for bonding semiconductor, method for mounting semiconductor chip and semiconductor device
JP2015137299A (en) * 2014-01-21 2015-07-30 住友ベークライト株式会社 Resin composition, adhesive sheet, adhesive sheet integrated with dicing tape, adhesive sheet integrated with back grind tape, adhesive sheet integrated with back grind tape also functioning as dicing tape, and electronic device
CN110819249A (en) * 2018-08-07 2020-02-21 日东电工株式会社 Back grinding belt

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
CN101689513A (en) * 2007-02-09 2010-03-31 Lg伊诺特有限公司 Multifunctional die attachment film and semiconductor packaging method using the same
JP2012054518A (en) * 2010-09-03 2012-03-15 Sekisui Chem Co Ltd Adhesive for bonding semiconductor, adhesive film for bonding semiconductor, method for mounting semiconductor chip and semiconductor device
JP2015137299A (en) * 2014-01-21 2015-07-30 住友ベークライト株式会社 Resin composition, adhesive sheet, adhesive sheet integrated with dicing tape, adhesive sheet integrated with back grind tape, adhesive sheet integrated with back grind tape also functioning as dicing tape, and electronic device
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