CN105899629A - Film-like adhesive, dicing tape with film-like adhesive, method for manufacturing semiconductor device, and semiconductor device - Google Patents

Film-like adhesive, dicing tape with film-like adhesive, method for manufacturing semiconductor device, and semiconductor device Download PDF

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Publication number
CN105899629A
CN105899629A CN201480072327.8A CN201480072327A CN105899629A CN 105899629 A CN105899629 A CN 105899629A CN 201480072327 A CN201480072327 A CN 201480072327A CN 105899629 A CN105899629 A CN 105899629A
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CN
China
Prior art keywords
particle
adhesive
membranaceous
membranaceous adhesive
weight
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
CN201480072327.8A
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Chinese (zh)
Inventor
菅生悠树
大西谦司
木村雄大
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.)
Nitto Denko Corp
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Nitto Denko 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
Priority claimed from JP2014001516A external-priority patent/JP2015129225A/en
Priority claimed from JP2014001531A external-priority patent/JP2015130418A/en
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of CN105899629A publication Critical patent/CN105899629A/en
Pending legal-status Critical Current

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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • 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
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0831—Gold
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • 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
    • C08K2201/001—Conductive additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • 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
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • 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
    • C09J2301/30—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
    • 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
    • C09J2301/314—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 the adhesive layer and/or the carrier being conductive
    • 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
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
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    • 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
    • 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
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    • 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
    • H01L2221/68377—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 with parts of the auxiliary support remaining in the finished device
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
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    • H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
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    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
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    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45117—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 400°C and less than 950°C
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    • H01—ELECTRIC ELEMENTS
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    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
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    • H01L2224/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L2224/80 - H01L2224/90
    • H01L2224/92—Specific sequence of method steps
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    • H01L2224/92247—Sequential connecting processes the first connecting process involving a layer connector the second connecting process involving a wire connector

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Dicing (AREA)

Abstract

Provided in the invention are: a film-like adhesive having excellent conductivity; and a dicing tape with a film-like adhesive. The present invention relates to a film-like adhesive which contains conductive particles having a specific shape. Examples of the conductive particles include gold particles, silver particles, copper particles and coated particles. Each of the coated particles is provided with a core particle and a coating film that covers the core particle. Examples of the material of the coating film include gold, silver and copper.

Description

Membranaceous adhesive, with membranaceous adhesive cutting belt, The manufacture method of semiconductor device and semiconductor device
Technical field
The present invention relates to membranaceous adhesive, the cutting belt with membranaceous adhesive, the system of semiconductor device Make method and semiconductor device.
Background technology
By method (institute gluing to semiconductor element and die-attach area etc. in the manufacture of semiconductor device The chip bonding method of meaning) from the beginning of conventional gold-silicon eutectic, developing into by solder, resin The method of glue.At present, the method using the resin glue using electric conductivity.
But, in the method using resin glue, there are and make electric conductivity reduction, resin because of space The problem that in uneven thickness, the pad of glue is contaminated because of oozing out of resin glue.In order to solve these Problem, sometimes replaces resin glue and uses the membranaceous adhesive containing polyimide resin (such as to join According to patent document 1).
On the other hand, it is also envisioned that power semiconductor arrangement in the market of semiconductor device in recent years Growth.In power semiconductor arrangement, high conductivity is required for element grafting material.
Prior art literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 6-145639 publication
Summary of the invention
Invent problem to be solved
First and second it is an object of the invention to, and solves described problem, it is provided that the film of excellent electric conductivity Shape adhesive, cutting belt with membranaceous adhesive.
For the method solving problem
First invention provides a kind of membranaceous adhesive, and it contains electroconductive particle, and electroconductive particle is In gold particle, silver particles, copper particle and coating particles at least a kind, coating particles possesses core Particle and the coating film of cladding core particle, coating film contains at least a kind in gold, silver and copper, Electroconductive particle contains the platy particle that aspect ratio is more than 5, in electroconductive particle 100 weight % The content of platy particle is 5 weight %～100 weight %.
If only coordinating spherical particle, then can form conductive path because of the point cantact between spherical particle. Different, in the membranaceous adhesive of first invention, generating plane contact between platy particle, thus Form conductive path.Thus, compared with the adhesive only coordinating spherical particle, it is possible to obtain excellent Electric conductivity.
Further, since platy particle contains gold, silver, copper etc., the electric conductivity of excellence therefore can be obtained.
Second present invention provides a kind of membranaceous adhesive, and it contains electroconductive particle, and electroconductive particle is In gold particle, silver particles, copper particle and coating particles at least a kind, coating particles possesses core Particle and the coating film of cladding core particle, coating film contains at least a kind in gold, silver and copper, Electroconductive particle contains spherical spherical particle, in the size distribution of spherical particle, exist 2 with On peak value, in the particle size range of 0.2 μm～0.8 μm, there is peak A, in 3 μm～15 μm Particle size range in there is peak value B, the particle diameter of peak value B is 5～15 with the ratio of the particle diameter of peak A.
In the membranaceous adhesive of second present invention, due to formed peak value B spherical particle between ( Gap), fill the spherical particle forming peak A, therefore form the contact point between multiple spherical particle. Therefore, it is possible to obtain excellent electric conductivity.
Further, since spherical particle contains gold, silver, copper etc., the electric conductivity of excellence therefore can be obtained.
Membranaceous adhesive obtains preferably by solvent coating method.This is because, the uniformity of thickness is excellent Different.
Membranaceous adhesive preferably comprises curable resin.Thus, it is possible to raising heat endurance.
The content of the electroconductive particle in membranaceous adhesive is preferably 30 weight %～95 weight %.If Less than 30 weight %, then have the trend being difficult to form conductive path.On the other hand, if more than 95 Weight %, then have the trend being difficult to membranization.It addition, have the trend that the closing force with wafer reduces.
The specific insulation of membranaceous adhesive is preferably 1 × 10-6More than Ω m and 9 × 10-2Ω m with Under.This is because, electric conductivity is good, can be highly suitable for Miniature high-density and install.
The thickness of membranaceous adhesive is preferably 5 μm～100 μm.Thus, viscous with semiconductor wafer etc. Junction is long-pending stable.It is additionally possible to suppress the oozing out of membranaceous adhesive.
Membranaceous adhesive uses preferably as chip adhesive film.
It addition, first and second present invention be provided with cutting belt and be laminated in cutting belt membranaceous The cutting belt with membranaceous adhesive of adhesive.
Under conditions of exfoliation temperature 25 DEG C, peeling rate 300mm/min, by membranaceous adhesive from cutting Cut peeling force when band is peeled off and be preferably 0.01N/20mm～3.00N/20mm.Thus, so that it may in case Only chip disperses, and can be picked up well simultaneously.
It addition, first and second present invention provides the manufacture method of a kind of semiconductor device, it includes making The operation of semiconductor chip is pasted with membranaceous adhesive chip on adherend.
It addition, first and second present invention provides a kind of semiconductor device.
By time gluing to membranaceous adhesive and substrate, can wait between membranaceous adhesive and substrate and mix Enter space.In the case of there is space between membranaceous adhesive and substrate, membranaceous adhesive with The area of substrate contact is little, and therefore conduction is low.
3rd it is an object of the invention to, and solves described problem, it is provided that can eliminate and be present in electric conductivity Space between membranaceous adhesive and adherend is it is thus possible to guarantee the membranaceous adhesive of electric conductivity and glued The membranaceous adhesive of area of thing contact, the cutting belt with membranaceous adhesive, the system of semiconductor device Make method.
3rd present invention provides a kind of membranaceous adhesive of electric conductivity, and it is for comprising partly leading of following operation The manufacture method of body device, i.e. press from both sides and engage half across the membranaceous adhesive of electric conductivity chip on adherend The operation of conductor chip, on adherend chip engage semiconductor chip operation after by pressurization The lower membranaceous adhesive of heating electric conductivity and be allowed to the operation of heat cure.
The membranaceous adhesive of electric conductivity of the 3rd present invention usually contains electroconductive particle.3rd present invention's The content of the electroconductive particle in the membranaceous adhesive of electric conductivity is preferably 30 weight %～95 weight %. If less than 30 weight %, then having the trend being difficult to form conductive path.On the other hand, if being more than 95 weight %, then have the trend being difficult to membranization.Reduce it addition, have the closing force with metal level Trend.
Consider from the reason of excellent electric conductivity, electroconductive particle be preferably selected from gold particle, silver particles, In copper particle and coating particles at least a kind.Coating particles possesses core particle and the bag of cladding core particle Overlay film.Coating film preferably comprises at least a kind in gold, silver and copper.
Preferably electroconductive particle contains the platy particle that aspect ratio is more than 5, electroconductive particle 100 The content of the platy particle in weight % is 5 weight %～100 weight %.
In the membranaceous adhesive of electric conductivity containing platy particle, generating plane contact between platy particle, by This forms conductive path.On the other hand, if only coordinating spherical particle, then can be because of spherical particle between Point cantact and form conductive path.Thus, the membranaceous adhesive of electric conductivity containing platy particle with only contain The adhesive having spherical particle is compared, it is possible to obtain excellent electric conductivity.
Electroconductive particle preferably comprises spherical spherical particle.Preferably in the size distribution of spherical particle In, there is the peak value of more than 2, in the particle size range of 0.2 μm～0.8 μm, there is peak A, Peak value B, the particle diameter of peak value B and the particle diameter of peak A is there is in the particle size range of 3 μm～15 μm Ratio be 5～15.
Size distribution exists in the membranaceous adhesive of electric conductivity of peak A and peak value B, due to Formed between the spherical particle of peak value B (gap), fill the spherical particle forming peak A, therefore The contact point between multiple spherical particle can be formed.Therefore, it is possible to obtain excellent electric conductivity.
It addition, the 3rd present invention provides the manufacture method of a kind of semiconductor device, comprising: folder across The membranaceous adhesive of electric conductivity on adherend chip engage the operation of semiconductor chip, on adherend core Make the membranaceous adhesive of electric conductivity by heating under elevated pressure after the operation of chip bonding semiconductor chip The operation of heat cure.
By making electric conductivity membranaceous adhesive heat cure under elevated pressure, can eliminate and be present in conductive film Space between shape adhesive and adherend, such that it is able to guarantee the membranaceous adhesive of electric conductivity and adherend The area of contact.Between semiconductor chip and adherend, electric current is flow through therefore, it is possible to easy to manufacture Semiconductor device.
In the operation making electric conductivity membranaceous adhesive heat cure, preferably at 0.5kg/cm2~ 20kg/cm2Pressure under heat.In the operation making electric conductivity membranaceous adhesive heat cure, excellent It is selected in the range of 80 DEG C～260 DEG C and heats.Additionally, it is preferred that at 0.1 hour～24 hours In the range of heat.
It addition, the 3rd present invention is provided with cutting belt and the conductive film being configured in cutting belt The cutting belt with membranaceous adhesive of shape adhesive.
The cutting belt with membranaceous adhesive of the 3rd present invention is used for including partly leading of following operation In the manufacture method of body device, i.e. the electric conductivity in the cutting belt with membranaceous adhesive is membranaceous gluing In agent, the operation of configuring semiconductor wafer, cutting are configured at the semiconductor die on the membranaceous adhesive of electric conductivity Sheet and form the operation of semiconductor chip, pick up together with membranaceous to semiconductor chip and electric conductivity adhesive Operation, folder across the membranaceous adhesive of electric conductivity on adherend chip engage semiconductor chip work Sequence and on adherend chip engage semiconductor chip operation after make by heating under elevated pressure The operation of electric conductivity membranaceous adhesive heat cure.
It addition, the 3rd present invention provides the manufacture method of a kind of semiconductor device including following operation, That is, the operation of the cutting belt with membranaceous adhesive is prepared, in the cutting belt with membranaceous adhesive The operation of configuring semiconductor wafer on the membranaceous adhesive of electric conductivity, that cutting is configured at electric conductivity is membranaceous gluing Semiconductor wafer in agent and form the operation of semiconductor chip, semiconductor chip is membranaceous with electric conductivity Operation, folder that adhesive picks up together engage half across the membranaceous adhesive of electric conductivity chip on adherend By adding after the operation of conductor chip and chip engages semiconductor chip on adherend operation Pressure is heated and is made the operation of electric conductivity membranaceous adhesive heat cure.
It addition, the 3rd present invention provides a kind of semiconductor device.
Invention effect
According to first and second present invention, it is provided that the membranaceous adhesive of excellent electric conductivity, with film The cutting belt of shape adhesive.
Accompanying drawing explanation
Fig. 1 is the constructed profile of the cutting belt with membranaceous adhesive.
Fig. 2 is the constructed profile of the cutting belt with membranaceous adhesive of variation.
Fig. 3 is the process profile of an example of the manufacture method for semiconductor device is described.
Fig. 4 is the constructed profile of membranaceous adhesive.
Fig. 5 is the constructed profile of the cutting belt with membranaceous adhesive.
Fig. 6 is the constructed profile of the cutting belt with membranaceous adhesive of variation.
Fig. 7 is the appearance representing and being configured with semiconductor wafer in the cutting belt with membranaceous adhesive The profile of outline.
Fig. 8 is the profile of the outline of the appearance after representing semiconductor wafer singualtion.
Fig. 9 is the constructed profile of the adherend with semiconductor chip.
Figure 10 is the constructed profile of semiconductor device.
Detailed description of the invention
[first invention]
The membranaceous adhesive of first invention contains electroconductive particle.As electroconductive particle, Ke Yiju Go out gold particle, silver particles, copper particle, coating particles etc..
Coating particles possesses core particle and the coating film of cladding core particle.Core particle can be electric conductivity, Dielectric any one, such as can use glass particle etc..As coating film, can enumerate Film containing gold, the film containing silver, the film etc. containing copper.
Electroconductive particle contains the platy particle that aspect ratio is more than 5.Due to for more than 5, therefore sheet It is susceptible to face contact between particle, conductive path can be readily formed.Aspect ratio be preferably 8 with On, more preferably more than 10.On the other hand, aspect ratio is preferably less than 10000, and more preferably 100 Hereinafter, more preferably less than 70, particularly preferably less than 50.
The aspect ratio of platy particle is ratio (the average major diameter/averagely thick of average major diameter and average thickness Degree).
In this specification, the average major diameter of platy particle is by utilizing scanning electron microscope (SEM) observe the section of membranaceous adhesive, measure the length of 100 platy particles randomly choosed Footpath and the mean value that obtains.
It addition, the average thickness of platy particle is by utilizing scanning electron microscope (SEM) Observe the section of membranaceous adhesive, measure the thickness of 100 platy particles randomly choosed and obtain Mean value.
The average major diameter of platy particle is preferably more than 0.5 μm, more than more preferably 1.0 μm.If Be more than 0.5 μm, then the contact probability of platy particle improves, and easily obtains conducting.
On the other hand, the average major diameter of platy particle is preferably below 50 μm, more preferably 30 μm Below.If below 50 μm, then it is difficult to produce the sedimentation of the particle in coating clear coat stage, permissible Make stable coating varnish.
Electroconductive particle can also be beyond platy particle, possibly together with acicular particles, filamentous particle, ball Shape particle etc..Wherein, consider from the reason obtaining high conductivity, preferably spherical particle.
The content of the platy particle in electroconductive particle 100 weight % is preferably more than 5 weight %, more It is preferably more than 10 weight %.The content of the platy particle in electroconductive particle 100 weight % also may be used Think 100 weight %, but below preferably 50 weight %, below more preferably 20 weight %.
The content of the spherical particle in electroconductive particle 100 weight % is preferably more than 50 weight %, more It is preferably more than 80 weight %.The content of the spherical particle in electroconductive particle 100 weight % is preferably Below 95 weight %, below more preferably 90 weight %.
The average grain diameter of electroconductive particle is not particularly limited, but relative to the thickness of membranaceous adhesive It is preferably more than 0.001 times (more than thickness × 0.001 of membranaceous adhesive), more preferably more than 0.1 times. If less than 0.001 times, then it is difficult to be formed conductive path, the trend of the conductive instability of meeting.It addition, The average grain diameter of electroconductive particle is preferably less than 1 times (membranaceous glue relative to the thickness of membranaceous adhesive Below the thickness of stick), more preferably less than 0.8 times.If more than 1 times, then have and cause chip to break The danger split.
And, the average grain diameter of electroconductive particle is to utilize the size distribution meter (HORIBA of luminosity formula System, device name；LA-910) value obtained.
The proportion of electroconductive particle is preferably more than 0.7, and more preferably more than 1.If less than 0.7, When then making adhesive compound solution (varnish), electroconductive particle can float, dividing of electroconductive particle Dissipate and likely become uneven.It addition, the proportion of electroconductive particle is preferably less than 22, more preferably It is less than 21.If more than 22, then electroconductive particle easily settles, and being dispersed with of electroconductive particle can Can become uneven.
The content of the electroconductive particle in membranaceous adhesive is preferably more than 30 weight %, and more preferably 40 More than weight %.If less than 30 weight %, then having the trend being difficult to form conductive path.It addition, The content of electroconductive particle is preferably below 95 weight %, below more preferably 94 weight %.If being more than 95 weight %, then have the trend being difficult to membranization.It addition, have becoming of the closing force reduction with wafer Gesture.
Membranaceous adhesive preferably comprises thermoplastic resin.As thermoplastic resin, natural rubber can be enumerated Glue, butyl rubber, isoprene rubber, neoprene, vinyl-vinyl acetate copolymer, second Alkene-acrylic copolymer, vinyl-acrylate copolymer, polybutadiene, polycarbonate resin Fat, thermoplastic polyimide resin, 6-nylon or 6, polyamide, the phenoxy group such as 6-nylon The saturated polyester resins such as resin, acrylic resin, PET or PBT, polyamide-imide resin, Or fluororesin etc..In the middle of these thermoplastic resins, particularly preferred ionic impurity is few and heat resistance is high, May insure that the acrylic resin of the reliability of semiconductor element.
As acrylic resin, be not particularly limited, can enumerate to have carbon number 30 with Under, particularly the alkyl of the straight or branched of carbon number 4～18 acrylic or methacrylic acid The one kind or two or more polymer as composition (acrylic copolymer) etc. of ester.As described Alkyl, such as, can enumerate methyl, ethyl, propyl group, isopropyl, normal-butyl, the tert-butyl group, isobutyl Base, amyl group, isopentyl, hexyl, heptyl, cyclohexyl, 2-ethylhexyl, octyl group, iso-octyl, Nonyl, different nonyl, decyl, isodecyl, undecyl, lauryl, tridecyl, myristyl, Stearyl, octadecyl or dodecyl etc..
It addition, as other monomers of formation polymer (acrylic copolymer), limit the most especially Fixed, such as can enumerate acrylic acid, methacrylic acid, carboxy ethyl acrylate, carboxypentyl acrylate, Such carboxyl group-containing monomer such as itaconic acid, maleic acid, fumaric acid or crotonic acid, maleic anhydride or clothing health Such anhydride monomers, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2 such as acid anhydrides -hydroxy propyl ester, (methyl) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid own ester of 6-hydroxyl, (methyl) acrylic acid 8-hydroxyl monooctyl ester, (methyl) acrylic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) third Such hydroxyl such as olefin(e) acid 12-hydroxylauric ester or acrylic acid (4-hydroxymethylcyclohexyl) methyl esters Monomer, styrene sulfonic acid, allyl sulfonic acid, 2-(methyl) acrylamide-2-methylpro panesulfonic acid, (methyl) acryamidopropanesulfonic acid, (methyl) acrylic acid sulphur propyl ester or (methyl) acryloyl-oxy Base naphthalene sulfonic acids etc. are such to be contained containing as sulfonic group monomer or acryloyl phosphoric acid 2-hydroxy methacrylate etc. Phosphate monomer.
In the middle of acrylic resin, preferable weight-average molecular weight is the resin of more than 100,000, more preferably The resin of 300000～3,000,000, the resin of further preferred 500,000～2,000,000.This is because, if For in above-mentioned number range, then cementability and excellent heat resistance.And, weight average molecular weight is to utilize The value that GPC (gel permeation chromatography) measures and utilizes polystyrene conversion to calculate.
The glass transition temperature of thermoplastic resin is preferably more than-40 DEG C, more preferably-35 DEG C with On, more preferably more than-25 DEG C.If less than-40 DEG C, the most membranaceous adhesive is tacky, and cuts Cut band to be excessively close to and have the trend that pick is deteriorated.It addition, the glass transition of thermoplastic resin Temperature is preferably less than-10 DEG C, more preferably less than-11 DEG C.If higher than-10 DEG C, then springform Quantitative change is high, has and is difficult to membranaceous adhesive attachment in semiconductor wafer in a low temperature of about 40 DEG C The trend of upper (low temperature attaching property reduces).
In this specification, the glass transition temperature of thermoplastic resin refers to utilize Fox formula to obtain Theoretical value.
It addition, as obtaining the additive method of glass transition temperature, the most with good grounds differential scanning amount Temperature during the maximum endothermic peak that heat meter (DSC) measures obtains the glass transition of thermoplastic resin The method of temperature.Specifically, by sample differential scanning calorimetry (DSC) (TA to be determined " Q-2000 " of Instrument company) (pre-at the glass transition temperature of the sample than prediction Testing temperature) temperature of high about 50 DEG C heats after 10 minutes, is cooled to the temperature of low 50 DEG C than predicted temperature And carry out pre-treatment, thereafter, in a nitrogen atmosphere, measure so that the programming rates of 5 DEG C/min heat up Heat absorption starting point temperature, as glass transition temperature.
Membranaceous adhesive preferably comprises the curable resins such as thermosetting resin.Thus, it is possible to it is steady to improve heat Qualitative.
As curable resin, can enumerate phenolic resin, amino resins, unsaturated polyester resin, Epoxy resin, polyurethane resin, silicones or thermoset polyimide resin etc..The most preferred The poor epoxy resin of the ionic impurity etc. of corrosion resistant semiconductor element.It addition, as asphalt mixtures modified by epoxy resin The preferred phenolic resin of curing agent of fat.
Be not particularly limited as epoxy resin, such as can use bisphenol A-type, bisphenol-f type, Bisphenol S type, bmminated bisphenol-A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, Fluorenes type, phenol novolac type, orthoresol novolac type, three (hydroxyphenyl) methane type, four (hydroxyls Phenyl) two functional epoxy resins such as ethane type or polyfunctional epoxy resin or hydantoins type, isocyanide The epoxy resin such as urea acid three-glycidyl ester type or glycidic amine type.Particularly preferably these epoxy resin In the middle of novolac type epoxy resin, biphenyl type epoxy resin, three (hydroxyphenyl) methane type resin Or four (hydroxyphenyl) ethane type epoxy resin.This is because, these epoxy resin are imbued with solid with conduct The reactivity of the phenolic resin of agent, the excellence such as heat resistance.
Phenolic resin is the material that the curing agent as epoxy resin plays a role, such as, can enumerate benzene Phenol linear phenolic resin, phenol aralkyl resin, cresol novalac resin, tert-butyl phenol are linear Novolac type phenolic resin, the first rank phenol aldehyde type phenol such as phenolic resin, nonyl phenol linear phenolic resin The polycarboxylated styrene such as urea formaldehyde, poly(4-hydroxystyrene) etc..Particularly preferably in the middle of these phenolic resin Phenol linear phenolic resin, phenol aralkyl resin.This is because, semiconductor device can be improved Connection reliability.
For the mixing ratio of epoxy resin Yu phenolic resin, the most preferably to become relative to epoxy resin The mode that every 1 equivalent epoxy radicals in Fen makes the hydroxyl in phenolic resin be 0.5～2.0 equivalents coordinates. More preferably 0.8～1.2 equivalents.I.e. because, if both mixing ratio depart from described scope, the most not Can carry out sufficient curing reaction, the characteristic of solidfied material easily deteriorates.
Membranaceous adhesive preferably comprises at the curable resin that 25 DEG C is solid and is aqueous at 25 DEG C Curable resin.Thus, it is possible to obtain good low temperature attaching property.
In this specification, so-called is aqueous at 25 DEG C, refers to that viscosity is less than 5000Pa when 25 DEG C ·s.On the other hand, so-called is solid at 25 DEG C, refer to when 25 DEG C viscosity be 5000Pa s with On.
And, viscosity can use the model HAAKE Roto of Thermo Scientific company VISCO1 measures.
In membranaceous adhesive, it is the solidification of solid during in curable resin 100 weight % 25 DEG C The content of property resin is preferably more than 10 weight %, more than more preferably 12 weight %.If being less than 10 weight %, the most membranaceous adhesive is tacky, has and is excessively close to cutting belt and makes pick be deteriorated Trend.
On the other hand, during 25 DEG C in curable resin 100 weight % it is the curable resin of solid Content be preferably below 60 weight %, below more preferably 30 weight %, more preferably Below 20 weight %.If more than 60 weight %, then having and be difficult to film in a low temperature of about 40 DEG C Shape adhesive attachment is the trend of (low temperature attaching property reduces) on semiconductor wafer.
Thermoplastic resin and the total content of curable resin in membranaceous adhesive are preferably 5 weights Amount more than %, more than more preferably 10 weight %.If more than 5 weight %, the most easily keep making Shape for film.It addition, the total content of thermoplastic resin and curable resin is preferably 70 weight % Hereinafter, below more preferably 60 weight %.If below 70 weight %, then electroconductive particle can be just Locality embodies electric conductivity.
In membranaceous adhesive, the weight of the weight/curable resin of thermoplastic resin is preferably 50/50～10/90, more preferably 40/60～15/85.If the ratio of thermoplastic resin is more than 50/50, Then have the trend that heat endurance is deteriorated.On the other hand, if the ratio of thermoplastic resin is less than 10/90, Then have the trend being difficult to membranization.
Membranaceous adhesive can also generally use when the most suitably containing manufacture film beyond described composition Compounding ingredient, such as crosslinking agent etc..
Membranaceous adhesive can utilize usual way manufacture.For example, it is possible to by making containing described The adhesive compound solution of each composition, by adhesive compound solution in the way of reaching given thickness Coat after forming coated film on base material partition, make this coated film be dried, and manufacture membranaceous adhesive.
As solvent used in adhesive compound solution, it is not particularly limited, however the most permissible Described each composition is dissolved equably, mixing or scattered organic solvent.Such as can enumerate dimethyl The ketone such as formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, acetone, MEK, cyclohexanone Class solvent, toluene, dimethylbenzene etc..Coating process is not particularly limited.As the method for solvent coating, Such as can enumerate die coating machine, gravure coater, roll coater, reverse roll coater, funny point-type scraper Coating machine, tubular type knife type coater, serigraphy etc..Wherein, high from the uniformity of coating thickness From the standpoint of, preferably die coating machine.
As base material partition, it is possible to use polyethylene terephthalate (PET), polyethylene, Polypropylene or utilize the remover such as fluorine class remover, chain alkyl esters of acrylic acid remover to carry out The plastic foil of surface coating or paper etc..As the coating process of adhesive compound solution, the most permissible Enumerate roller coat, silk screen coating, intaglio plate coating etc..It addition, the drying condition of coated film limits the most especially Fixed, such as can be to carry out the baking temperature of 70～160 DEG C, the drying time of 1～5 minute.
As the manufacture method of membranaceous adhesive, such as, it also is adapted for as described each composition mixer is mixed Close, by compressing for the mixture of gained and manufacture the method etc. of membranaceous adhesive.Can as mixer To enumerate planetary mixer etc..
The thickness of membranaceous adhesive is not particularly limited, but more than preferably 5 μm, more preferably More than 15 μm.If less than 5 μm, then semiconductor wafer or the semiconductor core that can produce with warpage occurs The position that sheet is non-glued, bond area can become unstable.It addition, the thickness of membranaceous adhesive is preferred It is below 100 μm, below more preferably 50 μm.If more than 100 μm, then can paste because of chip Load and make membranaceous adhesive exceedingly ooze out, thus pad can be polluted.
Membranaceous adhesive is pasted onto on minute surface silicon wafer rear, preferred at 25 DEG C of closing forces measured at 40 DEG C For more than 0.5N/10mm, more preferably more than 0.6N/10mm, more preferably 4N/10mm with On.If more than 0.5N/10mm, then can be by good for membranaceous adhesive in a low temperature of about 40 DEG C Therefore ground is gluing is possible to prevent the heat affecting to semiconductor wafer in semiconductor wafer, can suppress half The warpage of conductor wafer.On the other hand, if less than 0.5N/10mm, then closing force is low, semiconductor die Sheet is likely peeled off from membranaceous adhesive.The upper limit of closing force is not particularly limited, but for example, Below 10N/10mm.
In this specification, closing force refers to the stripping when minute surface silicon wafer is peeled off of the membranaceous adhesive Power, it is possible to use following method measures.
The mensuration of peeling force
Use 2kg roller, after membranaceous adhesive is pasted the minute surface silicon wafer of 40 DEG C, put at 40 DEG C Put 2 minutes.Thereafter, place 20 minutes at normal temperature (25 DEG C), obtain possessing membranaceous adhesive and viscous The sample of the minute surface silicon wafer being affixed on membranaceous adhesive.Use cupping machine ((strain) Shimadzu system Make made AGS-J) to sample with peel angle 180 degree, exfoliation temperature 25 DEG C, peeling rate 300mm/min measures the peeling force when minute surface silicon wafer peels off membranaceous adhesive.
The storage modulus of 25 DEG C of membranaceous adhesive is preferably more than 5MPa, and more preferably 2 × 102MPa Above.If less than 5MPa, then the closing force with cutting belt uprises, and pick has the trend of reduction. The storage modulus of 25 DEG C of membranaceous adhesive is preferably 5 × 103Below MPa, more preferably 3 × 103MPa Hereinafter, more preferably 2.5 × 103Below MPa.It is difficult to more than 5 × 10 on coordinating3MPa。
The storage modulus of 100 DEG C of membranaceous adhesive is preferably more than 0.01MPa, more preferably More than 0.05MPa.If more than 0.01MPa, then when chip is pasted, membranaceous adhesive is difficult to ooze out. On the other hand, the storage modulus of 100 DEG C of membranaceous adhesive is preferably below 1MPa, more preferably Below 0.8MPa.If below 1MPa, then chip is difficult to be involved in space when pasting, and is easily formed steady Fixed chip is pasted.
The surface roughness (Ra) of membranaceous adhesive is preferably 0.1～5000nm.If less than 0.1nm, Then difficulty on coordinating.On the other hand, if more than 5000nm, then low temperature attaching property is likely to decrease. It addition, the attaching with adherend when chip is pasted is likely to decrease.
The resistivity of membranaceous adhesive is the lowest more good, and for example, 9 × 10-2Below Ω m.If 9 × 10 -2 below Ω m, then electric conductivity is good, can tackle small-sized-high-density installation.Specific insulation is excellent Elect 1 × 10 as-2Below Ω m.On the other hand, resistivity is preferably 1 × 10-6More than Ω m.
And, specific insulation can utilize the method described in embodiment to measure.
The thermal conductivity of membranaceous adhesive is the highest more good, for example, more than 0.5W/m K.If More than 0.5W/m K, then thermal diffusivity is good, can tackle small-sized-high-density installation.On the other hand, If less than 0.5W/m K, then poor radiation, accumulation of heat, it is possible to make electric conductivity deteriorate.
Membranaceous adhesive goes for the manufacture of semiconductor device.Wherein, particularly may be adapted to make Make for the adherends such as lead frame and semiconductor chip being carried out the chip adhesive film of gluing (chip stickup) With.As adherend, lead frame, built-in inserted plate, semiconductor chip etc. can be enumerated.Wherein, preferably Lead frame.
Membranaceous adhesive preferably uses with the form of the cutting belt with membranaceous adhesive.If with this form Use, then can dispose the semiconductor die of the state being attached in the cutting belt with membranaceous adhesive Sheet, therefore can reduce the chance disposed with single semiconductor wafer, and the property disposed is good.Thus, Even slim semiconductor wafer in recent years, it is also possible to dispose well.It addition, with this form In the case of use, it is stickup semiconductor wafer on membranaceous adhesive, aforesaid yet with using Membranaceous adhesive, therefore can suppress the warpage of semiconductor wafer.
Cutting belt with membranaceous adhesive is illustrated.
As it is shown in figure 1, the cutting belt 10 with membranaceous adhesive possesses cutting belt 11 and stacking Membranaceous adhesive 3 in cutting belt 11.Cutting belt 11 possesses base material 1 and is laminated on base material 1 Adhesive phase 2.Membranaceous adhesive 3 is configured on adhesive phase 2.
As in figure 2 it is shown, the cutting belt 10 with membranaceous adhesive can also be only (partly to lead at workpiece Body wafer 4 etc.) attach the composition being formed in part with adhesive layer 3.
Base material 1 is the material of the intensity parent becoming the cutting belt 10 with membranaceous adhesive, preferably There is the material of UV transmissive.As base material 1, such as, can enumerate low density polyethylene (LDPE), straight Chain shaped polyethylene, medium density polyethylene, high density polyethylene (HDPE), ultra-low density polyethylene, random copolymerization The polyolefin such as polypropylene, block copolymerization polypropylene, HOPP, polybutene, polymethylpentene, Vinyl-vinyl acetate copolymer, ionomer resin, ethene-(methyl) acrylic copolymer, Ethene-(methyl) acrylate (random, alternately) copolymer, ethylene-butene copolymer, second Alkene-hexene copolymer, polyurethane, polyethylene terephthalate, PEN Deng polyester, Merlon, polyimides, polyether-ether-ketone, polyimides, PEI, polyamides Amine, fully aromatic polyamide, polyphenylene sulfide, aromatic polyamides (paper), glass, glass cloth, fluorine Resin, polyvinyl chloride, polyvinylidene chloride, cellulosic resin, silicones, metal (paper tinsel), Paper etc..
For the surface of base material 1, in order to improve adaptation with adjacent layer, retentivity etc., permissible Implementing usual surface to process, such as chromic acid process, ozone exposure, fire exposure, high-voltage electric shock are sudden and violent Dew, ionizing ray process etc. chemically or physically process, by silane coupling agent (adhesion substance the most described later) Coating process.
The thickness of base material 1 can the most suitably determine, generally 5～200 μm are left Right.
As adhesive used in the formation of adhesive phase 2, it is not particularly limited, such as, can make With the general pressure-sensitive adhesive such as acrylic adhesives, rubber adhesive.As pressure-sensitive adhesive, From the deterrent such as semiconductor wafer or glass pollute electronic unit by the organic solvent such as ultra-pure water, alcohol Cleaning washing performance etc. from the standpoint of, the preferably propylene of polymer based on acrylic polymer Acrylic binder.
As acrylic polymer, such as, can enumerate by (methyl) alkyl acrylate (such as Methyl esters, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, secondary butyl ester, the tert-butyl ester, pentyl ester, different Pentyl ester, own ester, heptyl ester, monooctyl ester, 2-Octyl Nitrite, different monooctyl ester, nonyl ester, ester in the last of the ten Heavenly stems, isodecyl ester, Undecyl ester, dodecyl ester, tridecyl ester, myristyl ester, cetyl ester, 18 The carbon number of the alkyl such as Arrcostab, eicosyl ester is 1～30, particularly carbon number be 4～ The straight-chain of 18 or the Arrcostab etc. of branched) and (methyl) acrylate base ester (such as ring Pentyl ester, cyclohexyl etc.) the one kind or two or more acrylic polymer used as monomer component Deng.And, so-called (methyl) acrylate, refer to acrylate and/or methacrylate, The what is called (methyl) of the present invention is identical meaning entirely.
Acrylic polymer can also be for the modified purpose of cohesiveness, heat resistance etc., according to need To contain and can become with other monomers of described (methyl) alkyl acrylate or cycloalkyl ester copolymerization Divide corresponding unit.As such monomer component, such as can enumerate acrylic acid, methacrylic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, itaconic acid, maleic acid, rich horse The carboxyl group-containing monomers such as acid, crotonic acid；The anhydride monomers such as maleic anhydride, itaconic anhydride；(methyl) third Olefin(e) acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxyl Base butyl ester, (methyl) acrylic acid own ester of 6-hydroxyl, (methyl) acrylic acid 8-hydroxyl monooctyl ester, (first Base) acrylic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) acrylic acid 12-hydroxy dodecyl acrylate, (methyl) The hydroxyl monomers such as acrylic acid (4-Hydroxymethyl-cyclo-hexyl) methyl esters；Styrene sulfonic acid, allyl sulphur Acid, 2-(methyl) acrylamide-2-methylpro panesulfonic acid, (methyl) acrylamido the third sulphur Acid, (methyl) acrylic acid sulphur propyl ester, (methyl) propane sulfonic acid etc. are containing sulfonic group monomer； The phosphorous acid-based monomers such as acryloyl phosphoric acid 2-hydroxy methacrylate；Acrylamide, acrylonitrile etc..These can Can use one kind or two or more with the monomer component of copolymerization.These can be with the use of the monomer of copolymerization Amount is preferably below 40 weight % of whole monomer components.
Additionally, in order to make acrylic polymer cross-link, it is also possible to as desired as comonomer Composition contains multi-functional monomer etc..As such multi-functional monomer, such as, can enumerate oneself two Alcohol two (methyl) acrylate, (gathering) ethylene glycol two (methyl) acrylate, (gathering) propane diols Two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite two (methyl) Acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) propylene Acid esters, dipentaerythritol six (methyl) acrylate, epoxy (methyl) acrylate, polyester (first Base) acrylate, carbamate (methyl) acrylate etc..These multi-functional monomers also may be used One kind or two or more to use.For the usage amount of multi-functional monomer, in terms of adhesion characteristic etc. Consider, below 30 weight % of whole monomer components.
Acrylic polymer can be by by single monomer or monomer mixture of more than two kinds in addition It is polymerized and obtains.Polymerization can utilize polymerisation in solution, emulsion polymerization, polymerisation in bulk, suspension polymerisation etc. Arbitrary mode is carried out.From the standpoint of pollution from the adherend prevented cleaning etc., low-molecular-weight thing The content of matter is the smaller the better.Considering from this point, the number-average molecular weight of acrylic polymer is preferably More than 300000, more preferably 400,000～about 3,000,000.
It addition, in described adhesive, for the acrylic polymer of polymer based on improving Deng number-average molecular weight, it is also possible to suitably use external crosslinker.Tool as outside cross-linking method The method of body, can enumerate interpolation polyisocyanate compounds, epoxide, aziridine cpd, The so-called crosslinking agents such as melamine class crosslinking agent the method being allowed to reaction.Using external crosslinker In the case of, its usage amount can according to the balance with the base polymer that should cross-link, further according to Use as adhesive suitably determines.It is said that in general, relative to described base polymer 100 weight portions, preferably coordinate below about 5 weight portions, more preferably coordinate 0.1～5 weight portions.This Outward, in adhesive, as required, it is also possible to outside described composition, also use existing known The additives such as various tackifier, age resister.
Adhesive phase 2 can utilize ray curing adhesive to be formed.Ray curing adhesive can Make the degree of cross linking increase with the irradiation because of rays such as ultraviolets, thus make its bonding force drop easily Low.
By only part 2a attaching part corresponding with workpiece of the adhesive phase 2 shown in Fig. 1 being entered Row radiation exposure, it is possible to the difference of the bonding force of setting and other part 2b.In the case of Gai, by Described part 2b that uncured ray curing adhesive is formed bonds with membranaceous adhesive 3, can To guarantee confining force when cutting.
It addition, by the adhesive making ray curing with the membranaceous adhesive 3 shown in Fig. 2 matchingly Layer 2 solidification, can form described part 2a that bonding force reduces significantly.In the case of Gai, permissible At the described part 2b fixed wafer ring formed by uncured ray curing adhesive.
That is, in the case of utilizing ray curing adhesive to form adhesive phase 2, preferably so that gluing The mode of the bonding force of bonding force other parts 2b of ＜ of described part 2a of mixture layer 2 is to described portion 2a is divided to carry out radiation exposure.
Ray curing adhesive can use rays such as having carbon-to-carbon double bond without particular limitation The functional group of curability and demonstrate the material of cohesive.As ray curing adhesive, example Can exemplify as described in contact adhesive acrylic adhesives, rubber adhesive etc. The ray curing of the addition type of the middle monomer component having coordinated ray-curable or oligomer composition glues Mixture.
As the monomer component of ray-curable joined together, such as, can enumerate carbamate oligomeric Thing, carbamate (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, Tetramethylol methane four (methyl) acrylate, pentaerythrite three (methyl) acrylate, season penta Tetrol four (methyl) acrylate, dipentaerythritol monohydroxy five (methyl) acrylate, two seasons Penta tetrol six (methyl) acrylate, BDO two (methyl) acrylate etc..It addition, The oligomer composition of ray-curable can enumerate carbamates, polyethers, polyesters, poly-carbon The various oligomer such as esters of gallic acid, polybutadiene, being suitably for its molecular weight is 100～about 30000 The oligomer of scope.The monomer component of ray-curable or the use level of oligomer composition can bases The kind of described adhesive phase, is suitably defined as reducing the amount of the bonding force of adhesive phase.One For as, relative to constituting base polymer 100 weight portion such as acrylic polymer of adhesive, For example, 5～500 weight portions, about preferably 40～150 weight portions.
It addition, as ray curing adhesive, except the actinic radiation-curable of the described addition type illustrated Beyond type adhesive, it is also possible to based on enumerating, polymer employs in polymer lateral chain or main chain Or main chain terminal has the ray curing adhesive of the inherent type of the polymer of carbon-to-carbon double bond.In Ray curing adhesive in type need not containing the oligomer composition etc. as low molecular composition, or Person need not be contained in a large number, moves within the adhesive layer thus without there being oligomer composition etc. to elapse in time Situation, the adhesive phase of the Rotating fields of stabilisation can be formed, the most preferably.
The described base polymer with carbon-to-carbon double bond can use without particular limitation has carbon -carbon double bond and there is the polymer of cohesive.As such base polymer, preferably with third Olefin(e) acid base polymer is as the polymer of basic framework.As the basic framework of acrylic polymer, The most illustrated acrylic polymer can be enumerated.
Carbon-to-carbon double bond introductory technique in described acrylic polymer is not particularly limited, and can adopt Use various method, and it is easy in MOLECULE DESIGN that carbon-to-carbon double bond imports polymer lateral chain.Such as, After the monomer that makes in advance there is functional group and acrylic polymer copolymerization can be enumerated, maintain carbon- Make while the ray-curable of carbon double bond to have can with the functional group of this functional group reactions and carbon- The compound of carbon double bond carries out the method for polycondensation or addition reaction.
As the example of the combination of these functional groups, can enumerate carboxylic acid group and epoxy radicals, carboxylic acid group with '-aziridino, hydroxyl and NCO etc..In the combination of these functional groups, from following response Easness considers, is suitably for the combination of hydroxyl and NCO.As long as it addition, by these officials There is described in the combination producing that can roll into a ball the combination of the acrylic polymer of carbon-to-carbon double bond, then functional group Be in acrylic polymer and described compound which side can, and at described preferred group In conjunction, be suitably for acrylic polymer and have hydroxyl, described compound has the feelings of NCO Condition.In the case of Gai, as having the isocyanate compound of carbon-to-carbon double bond, such as, can enumerate first Base propenoyl isocyanate, 2-methacryloxyethyl isocyanates, an isopropenyl- Alpha, alpha-dimethylbenzyl isocyanates etc..It addition, as acrylic polymer, it is possible to use By hydroxyl monomer or 2-hydroxyethyl vinyl ether, the 4-hydroxybutyl vinyl base of described illustration Ether, diethylene glycol monovinyl base ether the copolymerization such as ether compound obtained by polymer.
The ray curing adhesive of described inherent type has carbon-to-carbon pair described in can being used alone The base polymer (particularly acrylic polymer) of key, but can also deteriorate not make characteristic Degree coordinate the monomer component of described ray-curable or oligomer composition.Ray-curable oligomeric It is in the range of 30 weight portions that thing composition etc. is commonly angled relative to base polymer 100 weight portion, preferably It it is the scope of 0～10 weight portions.
In described ray curing adhesive, contain in the case of utilizing ultraviolet etc. to be allowed to solidification Photoepolymerizationinitiater initiater.As Photoepolymerizationinitiater initiater, such as, can enumerate 4-(2-hydroxyl-oxethyl) Phenyl (2-hydroxyl-2-propyl group) ketone, Alpha-hydroxy-α, α '-dimethyl acetophenone, 2-first The α-one alcohol compounds such as base-2-hydroxypropiophenonepreparation, 1-hydroxycyclohexylphenylketone；Methoxyl group Acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenone, 2 The acetophenones such as-methyl isophthalic acid-[4-(methyl mercapto)-phenyl]-2-morpholinopropane-1-ketone Compounds；The benzoin ethers chemical combination such as benzoin ethyl ether, benzoin iso-propylether, anisoin methyl ether Thing；The ketal compounds such as dibenzoyl dimethyl ketal；The aromatic sulfonyl classes such as 2-naphthalene sulfonyl chloride Compound；1-phenyl-1, the photolytic activity oxime such as 1-propanedione-2-(O-ethoxy carbonyl) oxime Compounds；Benzophenone, benzoyl benzoic acid, 3,3 '-dimethyl-4-methoxyl group hexichol The benzophenone compounds such as ketone；Thioxanthones, CTX, 2-methyl thioxanthones, 2,4 -dimethyl thioxanthone, isopropyl thioxanthone, 2,4-bis-clopenthixal ketone, 2,4-diethyl thioxanthene Ketone, 2, the thioxanthones compounds such as 4-diisopropylthioxanthone；Camphorone；Halogenated ketone；Acylphosphanes Oxide；Acyl phosphonate etc..The use level of Photoepolymerizationinitiater initiater is relative to the propylene constituting adhesive The base polymers such as acids polymers 100 weight portion, about for example, 0.05～20 weight portions.
It addition, as ray curing adhesive, such as Japanese Laid-Open Patent Publication 60-196956 can be enumerated Disclosed in number publication, containing the addition polymerization compound of unsaturated bond, the tool with more than 2 The photopolymerizable compound such as the alkoxy silane having epoxy radicals and carbonyls, organosulfur compound, The rubber adhesive of the Photoepolymerizationinitiater initiaters such as peroxide, amine, salt compounds or acrylic compounds Adhesive etc..
In the adhesive phase 2 of described ray curing, as required, it is also possible to shine containing because of ray The compound penetrated and colour.By making in adhesive phase 2 containing the chemical combination coloured because of radiation exposure Thing, the colored parts that can only will be irradiated.The compound coloured because of radiation exposure is to penetrate Line pre-irradiation is colourless or light color, becomes coloured compound because of radiation exposure, such as, can enumerate Leuco dye etc..The use ratio of the compound coloured because of radiation exposure can suitably set.
The thickness of adhesive phase 2 is not particularly limited, but from preventing the defect of chip section, guarantor From the standpoint of holding the fixing property taken into account etc. of adhesive layer, about preferably 1～50 μm.More preferably 2～30 μm, more preferably 5～25 μm.
Membranaceous adhesive 3 with the cutting belt 10 of membranaceous adhesive preferably (is not schemed by partition protection Show).Partition had before applying the merit as protection material protecting membranaceous adhesive 3 for reality Energy.Partition is peeled when being fitted in by workpiece on membranaceous adhesive 3.As partition, it is possible to so that With polyethylene terephthalate (PET), polyethylene, polypropylene or utilize fluorine class remover, The removers such as chain alkyl esters of acrylic acid remover have carried out plastic foil or the paper etc. of surface coating.
Cutting belt 10 with membranaceous adhesive can utilize usual way manufacture.Such as, by inciting somebody to action The adhesive phase 2 of cutting belt 11 is fitted with membranaceous adhesive 3, can manufacture cutting with membranaceous adhesive Cut band 10.
Under conditions of exfoliation temperature 25 DEG C, peeling rate 300mm/min, by membranaceous adhesive 3 from Peeling force (peak load) when cutting belt 11 is peeled off is preferably 0.01～3.00N/20mm.If it is little In 0.01N/20mm, then likely produce chip during cutting and disperse.On the other hand, if being more than 3.00N/20mm, then have pickup and become the trend of difficulty.
Under conditions of exfoliation temperature 25 DEG C, peeling rate 300mm/min, by membranaceous adhesive 3 from Peeling force when cutting belt 11 is peeled off can utilize the method described in embodiment to measure.
While with reference to Fig. 3, manufacture semiconductor dress to using the cutting belt 10 with membranaceous adhesive One example of the method put illustrates.
First, semiconductor wafer 4 is crimped on the membranaceous gluing of the cutting belt 10 with membranaceous adhesive The semiconductor wafer of agent 3 attaches in part 3a, is allowed to gluing holding and fixes (attaching operation).This work Sequence is to carry out while utilizing the press tool pressings such as crimping roller.At this point it is possible at about 40 DEG C Crimp under low temperature.Specifically, crimping temperature (attaching temperature) is preferably more than 35 DEG C, more preferably It it is more than 37 DEG C.The upper limit preferably crimping temperature is low, preferably less than 50 DEG C, more preferably 45 DEG C with Under, more preferably less than 43 DEG C.Owing to semiconductor can be attached in a low temperature of about 40 DEG C On crystal 4, therefore it is possible to prevent the heat affecting to semiconductor wafer 4, such that it is able to suppression semiconductor die The warpage of sheet 4.
It addition, pressure is preferably 1 × 105～1 × 107Pa, more preferably 2 × 105～8 × 106Pa.It addition, As the time of attaching, preferably 1 second～5 minutes, more preferably 1 minute～3 minutes.
Then, the cutting of semiconductor wafer 4 is carried out.Thus, semiconductor wafer 4 is cut into given Size and singualtion, produce semiconductor chip 5.Cutting such as can be from the circuit of semiconductor wafer 4 Side, face is carried out according to well-established law.It addition, in this operation, such as can use and be cut into membranaceous gluing The cutting mode etc. being referred to as entirely cutting of the cutting belt 10 of agent.As cutter sweep used in this operation It is not particularly limited, it is possible to use existing known cutter sweep.Further, since semiconductor wafer 4 Gluing fixing by the cutting belt 10 with membranaceous adhesive, chip defect or chip therefore can be suppressed to fly Dissipate, the breakage of semiconductor wafer 4 can also be suppressed simultaneously.
In order to the semiconductor chip 5 in the gluing cutting belt 10 being fixed on membranaceous adhesive is shelled From, carry out the pickup of semiconductor chip 5.Method as pickup is not particularly limited, and can use Existing known various methods.For example, it is possible to enumerate each semiconductor chip 5 with pin from film The cutting belt 10 side jack-up of shape adhesive, utilize pick device pickup by the semiconductor chip 5 of jack-up Method etc..
Here, in the case of adhesive phase 2 is ultraviolet hardening, this adhesive phase 2 is being irradiated It is picked up after ultraviolet.Thus, the bonding force of membranaceous adhesive 3 is reduced by adhesive phase 2, partly leads The stripping of body chip 5 becomes easy.As a result, it is possible to do not damage the pickup of semiconductor chip 5 ground.Purple Exposure intensity, the condition such as irradiation time when outside line is irradiated are not particularly limited, if suitably basis Needs set.
The semiconductor chip 5 picked up is pressed from both sides and is fixed on adherend 6 across membranaceous adhesive 3 is gluing (chip stickup).
Chip sticking temperature is preferably more than 80 DEG C, more preferably more than 90 DEG C.It addition, chip is pasted Temperature is preferably less than 150 DEG C, more preferably less than 130 DEG C.By being set to less than 150 DEG C, permissible The generation of the warpage after preventing chip from pasting.
It follows that utilize heating to make the heat cure of membranaceous adhesive 3, make semiconductor chip 5 and adherend 6 Gluing.Make the heat cure of membranaceous adhesive 3 preferably by the heating under pressured atmosphere, make semiconductor chip 5 Gluing with adherend 6.By making the heat cure of membranaceous adhesive 3 under pressured atmosphere, existence can be eliminated Space between membranaceous adhesive 3 and adherend 6, such that it is able to guarantee membranaceous adhesive 3 and glued The area of thing 6 contact.
The pressure of pressured atmosphere is preferably 0.5kg/cm2(4.9×10-2MPa) more than, more preferably 1kg/cm2(9.8×10-2MPa) more than, more preferably 5kg/cm2(4.9×10-1MPa) with On.If 0.5kg/cm2Above, then can easily eliminate and be present in membranaceous adhesive 3 and adherend Space between 6.The pressure of pressured atmosphere is preferably 20kg/cm2(1.96MPa) below, more preferably For 18kg/cm2(1.77MPa) below, more preferably 15kg/cm2(1.47MPa) below. If 20kg/cm2Hereinafter, then oozing out of the membranaceous adhesive 3 caused by excessive pressurization can be suppressed.
The temperature heated is preferably more than 80 DEG C, more preferably more than 170 DEG C.Heat Temperature is preferably less than 200 DEG C, more preferably less than 180 DEG C.If the temperature heated is above-mentioned model Enclose, then can be the most gluing.It addition, the time heated can suitably set.
Then, carry out the front end of the portion of terminal (inner lead) of adherend 6 and semiconductor chip 5 On electrode pad (not shown) utilize the wire bond operation that bonding wire 7 electrically connects.As bonding wire 7, such as Gold thread, aluminum steel or copper cash etc. can be used.Temperature when carrying out wire bond is preferably more than 80 DEG C, more excellent Electing more than 120 DEG C as, this temperature is preferably less than 250 DEG C, more preferably less than 175 DEG C.It addition, Its heat time is several seconds～several minutes (such as 1 second～1 minute).Wiring is to be heated to be described temperature Under state in the range of degree, can be entered with crimping of pressurization by the vibrational energy being applied in combination ultrasonic wave OK.
It follows that carry out the sealing process utilizing sealing resin 8 to be sealed by semiconductor chip 5.This operation It is in order to protect the semiconductor chip 5 being equipped on adherend 6, bonding wire 7 and to carry out.This operation is logical Cross and with mould, the resin forming sealed is carried out.As sealing resin 8, such as, use epoxies Resin.Heating-up temperature during resin seal is preferably more than 165 DEG C, more preferably more than 170 DEG C, This heating-up temperature is preferably less than 185 DEG C, more preferably less than 180 DEG C.
As required, it is also possible to sealer is heated further (rear curing process).Thus, so that it may So that the sealing resin 8 solidifying deficiency in sealing process is fully cured.Heating-up temperature can suitably set Fixed.
The membranaceous adhesive 3 of use chip stickup semiconductor on adherend 6 is comprised as it has been described above, utilize The method of the operation of chip 5, it is possible to produce semiconductor device.That is, utilize comprise will be provided with membranaceous Adhesive 3 and the chip joint chip of semiconductor chip 5 contacted with membranaceous adhesive 3 are crimped on The method of the operation on adherend 6, it is possible to produce semiconductor device.
Such as, utilization is included in and configures with on the membranaceous adhesive 3 of the cutting belt 10 of membranaceous adhesive Operation I of semiconductor wafer 4, cutting are configured at the semiconductor wafer 4 on membranaceous adhesive 3 and form half Operation II of conductor chip 5, by utilize operation II to be formed semiconductor chip 5 together with membranaceous adhesive 3 Pickup operation III and the semiconductor chip 5 utilizing operation III to pick up is pressed from both sides across membranaceous adhesive 3 On adherend 6, the method for operation IV that chip is pasted, can produce semiconductor device suitably.
Above, it is described with first.
[second present invention]
Second present invention is identical with first invention in addition to electroconductive particle.Therefore, the most right Electroconductive particle illustrates.
The membranaceous adhesive of second present invention contains electroconductive particle.As electroconductive particle, Ke Yiju Go out gold particle, silver particles, copper particle, coating particles etc..
Coating particles possesses core particle and the coating film of cladding core particle.Core particle can be electric conductivity, Dielectric any one, such as can use glass particle etc..As coating film, can enumerate Film containing gold, the film containing silver, the film etc. containing copper.
Electroconductive particle contains spherical spherical particle.
In the size distribution of spherical particle, at least there is peak A and peak value B.Specifically, exist There is peak A in the particle size range of 0.2 μm～0.8 μm, exist in the particle size range of 3 μm～15 μm Peak value B.In membranaceous adhesive, between the spherical particle forming peak value B, fill and form peak A Spherical particle, be consequently formed the contact point between multiple spherical particle.Therefore, it is possible to obtain excellence Electric conductivity.
Owing to peak A is present in the particle size range of more than 0.2 μm, therefore, it is difficult to there is spherical particle Between cohesion.
Preferred peak A is present in the particle size range of more than 0.5 μm.
Owing to peak A is present in the particle size range of below 0.8 μm, therefore peak value B can formed Spherical particle between, fill formed peak A spherical particle.Preferred peak A is present in 0.75 μm In following particle size range.
Owing to peak value B is present in the particle size range of more than 3 μm, therefore can form peak value B's Between spherical particle, fill the spherical particle forming peak A.Preferred peak B is present in more than 3.5 μm Particle size range in.
Owing to peak value B is present in the particle size range of below 15 μm, when therefore can suppress to make membranaceous Surface roughness, can be allowed to the most bonding with adherend.Preferred peak B is present in 10 μm In following particle size range, it is more preferably the presence of in the particle size range below 8 μm, further preferably deposits It is in the particle size range of below 6 μm.
The particle diameter of peak value B is 5 with the ratio (particle diameter of the particle diameter/peak A of peak value B) of the particle diameter of peak A Above, preferably more than 7.Due to for more than 5, therefore can formed peak value B spherical particle it Between, fill the spherical particle forming peak A.
On the other hand, the particle diameter of peak value B is less than 15 with the ratio of the particle diameter of peak A, preferably 10 with Under.Owing to for less than 15, therefore spherical particle can be filled with high density.
In the size distribution of spherical particle, it is also possible to there is the peak beyond peak A and peak value B.
And, the size distribution of spherical particle can utilize the method described in embodiment to measure.
The average grain diameter of spherical particle is preferably more than 1 μm, more than more preferably 1.5 μm.If 1 μm Above, then good concavo-convex tracing ability can be obtained.It addition, the average grain diameter of spherical particle is preferably Below 10 μm, below more preferably 8 μm, more preferably below 5 μm.If below 10 μm, Then film formability is good.
And, the average grain diameter of spherical particle can utilize the method described in embodiment to measure.
Electroconductive particle can also be beyond spherical particle, possibly together with acicular particles, filamentous particle, sheet Shape particle etc..
The content of the spherical particle in electroconductive particle 100 weight % is preferably more than 5 weight %, more excellent Elect more than 80 weight % as, more preferably more than 90 weight %, particularly preferably 100 weight %.
Explanation in the suitable average grain diameter of electroconductive particle, suitable proportion such as the first membranaceous adhesive Shown in.
Suitably in the membranaceous adhesive of content such as first of electroconductive particle shown in explanation.
Above, it is described with second.
[the 3rd present invention]
As shown in Figure 4, the form of membranaceous adhesive 103 is membranaceous.Membranaceous adhesive 103 possesses conduction Property and thermosetting.About membranaceous gluing with first and second present invention of the explanation of membranaceous adhesive 103 Agent is identical.Thus, for membranaceous adhesive 103, illustrate simply.
Membranaceous adhesive 103 preferably comprises thermoplastic resin.As thermoplastic resin, sky can be enumerated So rubber, butyl rubber, isoprene rubber, neoprene, vinyl-vinyl acetate copolymer, Ethylene-acrylic acid copolymer, vinyl-acrylate copolymer, polybutadiene, Merlon Resin, thermoplastic polyimide resin, 6-nylon or 6, polyamide, the benzene oxygen such as 6-nylon Saturated polyester resin, the polyamidoimide trees such as base resin, acrylic resin, PET or PBT Fat or fluororesin etc..In the middle of these thermoplastic resins, particularly preferred ionic impurity is few and heat resistance High, may insure that the acrylic resin of the reliability of semiconductor element.
The glass transition temperature of thermoplastic resin is preferably more than-40 DEG C, more preferably-35 DEG C with On, more preferably more than-25 DEG C.If less than-40 DEG C, the most membranaceous adhesive 103 is tacky, Excessively it is close to cutting belt and has the trend that pick is deteriorated.It addition, the vitrifying of thermoplastic resin Transition temperature is preferably less than-5 DEG C, more preferably less than-10 DEG C, more preferably-11 DEG C Below.If higher than-10 DEG C, then elastic modelling quantity uprises, and has and is difficult in a low temperature of about 40 DEG C Membranaceous adhesive 103 is attached on semiconductor wafer the trend of (low temperature attaching property reduces).It addition, If the glass transition temperature of thermoplastic resin is less than-5 DEG C, then can improve heat curing temperature attached The mobility of near membranaceous adhesive 103, easily utilizes the heating under pressure to eliminate space.
Membranaceous adhesive 103 preferably comprises the curable resins such as thermosetting resin.Thus, it is possible to improve Heat endurance.
As curable resin, can enumerate phenolic resin, amino resins, unsaturated polyester resin, Epoxy resin, polyurethane resin, silicones or thermoset polyimide resin etc..The most preferred The poor epoxy resin of the ionic impurity etc. of corrosion resistant semiconductor element.It addition, as asphalt mixtures modified by epoxy resin The preferred phenolic resin of curing agent of fat.
For the mixing ratio of epoxy resin Yu phenolic resin, the most preferably to become relative to epoxy resin The mode that every 1 equivalent epoxy radicals in Fen makes the hydroxyl in phenolic resin be 0.5～2.0 equivalents coordinates. More preferably 0.8～1.2 equivalents.I.e. because, if both mixing ratio depart from described scope, the most not Can carry out sufficient curing reaction, the characteristic of solidfied material easily deteriorates.
Membranaceous adhesive 103 preferably comprises at the curable resin that 25 DEG C is solid and is liquid at 25 DEG C The curable resin of shape.Thus, it is possible to obtain good low temperature attaching property.
In membranaceous adhesive 103, it is solid during in curable resin 100 weight % 25 DEG C The content of curable resin is preferably more than 10 weight %, more than more preferably 12 weight %.If it is little In 10 weight %, the most membranaceous adhesive 103 is tacky, has and is excessively close to cutting belt and makes pickup Property be deteriorated trend.On the other hand, it is solid during 25 DEG C in curable resin 100 weight % The content of curable resin is preferably below 60 weight %, below more preferably 30 weight %, enters one Step is preferably below 20 weight %.If more than 60 weight %, then having the low temperature at about 40 DEG C Under be difficult to be attached on semiconductor wafer membranaceous adhesive 103 trend of (low temperature attaches property to be reduced).
Thermoplastic resin and the total content of curable resin in membranaceous adhesive 103 are preferably 5 More than weight %, more than more preferably 10 weight %.If more than 5 weight %, the most easily keeping Shape as film.It addition, the total content of thermoplastic resin and curable resin is preferably 70 weights Amount below %, below more preferably 60 weight %.If below 70 weight %, then electroconductive particle Electric conductivity can be embodied rightly.
In membranaceous adhesive 103, the weight of the weight/curable resin of thermoplastic resin is preferably 50/50～10/90, more preferably 40/60～15/85.If the ratio of thermoplastic resin is more than 50/50, Then have the trend that heat endurance is deteriorated.On the other hand, if the ratio of thermoplastic resin is less than 10/90, Then have the trend being difficult to membranization.
Membranaceous adhesive 103 preferably comprises electroconductive particle.Thus, it is possible to give electric conductivity.Make For electroconductive particle, gold particle, silver particles, copper particle, coating particles etc. can be enumerated.
Coating particles possesses core particle and the coating film of cladding core particle.Core particle can be electric conductivity, Dielectric any one, such as can use glass particle etc..As coating film, can enumerate Film containing gold, the film containing silver, the film etc. containing copper.
The average grain diameter of electroconductive particle is not particularly limited, but preferably with respect to membranaceous adhesive The thickness of 103 is more than 0.001 times (more than thickness × 0.001 of membranaceous adhesive 103), more excellent Elect more than 0.1 times as.If less than 0.001 times, being then difficult to be formed conductive path, meeting is conductive not Stable trend.It addition, the average grain diameter of electroconductive particle is preferably with respect to membranaceous adhesive 103 Thickness be less than 1 times (below the thickness of membranaceous adhesive 103), more preferably less than 0.8 times. If more than 1 times, then having the danger causing chip rupture.
And, the average grain diameter of electroconductive particle is to utilize the size distribution meter (HORIBA of luminosity formula System, device name；LA-910) value obtained.
The proportion of electroconductive particle is preferably more than 0.7, and more preferably more than 1.If less than 0.7, When then making adhesive compound solution (varnish), electroconductive particle can float, dividing of electroconductive particle Dissipate and likely become uneven.It addition, the proportion of electroconductive particle is preferably less than 22, more preferably It is less than 21.If more than 22, then electroconductive particle easily settles, and being dispersed with of electroconductive particle can Can become uneven.
Electroconductive particle can contain platy particle, spherical particle, acicular particles, filamentous particle etc.. Wherein, electroconductive particle preferably comprises platy particle, spherical particle.
As platy particle, such as, can enumerate the particle of the sheet that aspect ratio is more than 5.If 5 Above, then it is susceptible to face contact between platy particle, conductive path can be readily formed.
Aspect ratio is preferably more than 8, and more preferably more than 10.On the other hand, aspect ratio is preferably Less than 10000, more preferably less than 100, more preferably less than 70, particularly preferably 50 Below.
The aspect ratio of platy particle is ratio (the average major diameter/averagely thick of average major diameter and average thickness Degree).
The average major diameter of platy particle is preferably more than 0.5 μm, more than more preferably 1.0 μm.If Be more than 0.5 μm, then the contact probability of platy particle improves, and easily obtains conducting.On the other hand, The average major diameter of platy particle is preferably below 50 μm, below more preferably 30 μm.If 50 μm Hereinafter, then it is difficult to produce the sedimentation of the particle in coating clear coat stage, stable coating can be made clear Paint.
The content of the platy particle in electroconductive particle 100 weight % is preferably more than 5 weight %, more excellent Elect more than 10 weight % as.The content of the platy particle in electroconductive particle 100 weight % can also be 100 weight %, but below preferably 50 weight %, below more preferably 20 weight %.
Electroconductive particle preferably comprises spherical spherical particle.
Preferably in the size distribution of spherical particle, at least there is peak A and peak value B.Such as, excellent It is selected in the particle size range of 0.2 μm～0.8 μm and there is peak A, in the particle size range of 3 μm～15 μm There is peak value B.In membranaceous adhesive 103, between the spherical particle forming peak value B, fill and formed The spherical particle of peak A, is consequently formed the contact point between multiple spherical particle.Therefore, it is possible to obtain Obtain excellent electric conductivity.
If peak A is present in the particle size range of more than 0.2 μm, then it is difficult to occur between spherical particle Cohesion.
Preferred peak A is present in the particle size range of more than 0.5 μm.
If peak A is present in the particle size range of below 0.8 μm, then can form the spherical of peak value B Between particle, fill the spherical particle forming peak A.Preferred peak A is present in below 0.75 μm In particle size range.
If peak value B is present in the particle size range of more than 3 μm, then can form the spherical of peak value B Between particle, fill the spherical particle forming peak A.Preferred peak B is present in the grain of more than 3.5 μm In the scope of footpath.
If peak value B is present in the particle size range of below 15 μm, then can suppress table when making membranaceous Surface roughness, can be allowed to the most bonding with adherend.Preferred peak B is present in below 10 μm In particle size range, it is more preferably the presence of in the particle size range below 8 μm, is further preferably present in In particle size range below 6 μm.
The particle diameter of peak value B is 5 with the ratio (particle diameter of the particle diameter/peak A of peak value B) of the particle diameter of peak A Above, preferably more than 7.If more than 5, then can formed peak value B spherical particle between, Fill the spherical particle forming peak A.
On the other hand, the particle diameter of peak value B is less than 15 with the ratio of the particle diameter of peak A, preferably 10 with Under.If less than 15, then can fill spherical particle with high density.
In the size distribution of spherical particle, it is also possible to there is the peak beyond peak A and peak value B.
The average grain diameter of spherical particle is preferably more than 1 μm, more than more preferably 1.5 μm.If 1 μm Above, then good concavo-convex tracing ability can be obtained.It addition, the average grain diameter of spherical particle is preferably Below 10 μm, below more preferably 8 μm, more preferably below 5 μm.If below 10 μm, Then film formability is good.
And, the size distribution of spherical particle and average grain diameter can utilize following method to measure.
The size distribution of spherical particle and the mensuration of average grain diameter
Membranaceous adhesive 103 is put into crucible, applies heat-flash and make membranaceous adhesive 103 be ashed.Will The ash content of gained carries out 10 minutes ultrasonic waves and processes after being scattered in pure water, use laser diffraction and scattering Formula particle size distribution device (Beckman Coulter Inc.'s system, " LS 13 320 "；Damp process) Obtain size distribution (volume reference) and average grain diameter.
The content of the spherical particle in electroconductive particle 100 weight % is preferably more than 5 weight %, more excellent Elect more than 80 weight % as, more preferably more than 90 weight %, particularly preferably 100 weight %.
The content of the electroconductive particle in membranaceous adhesive 103 is preferably more than 30 weight %, more preferably It is more than 40 weight %, more preferably more than 60 weight %, more than particularly preferably 70 weight %. If less than 30 weight %, then having the trend being difficult to form conductive path.It addition, electroconductive particle Content is preferably below 95 weight %, below more preferably 94 weight %.If more than 95 weight %, then Have the trend being difficult to membranization.It addition, have the trend that closing force reduces.
Membranaceous adhesive 103 can also the most suitably contain during manufacture film general beyond described composition The compounding ingredient used, such as crosslinking agent etc..
Membranaceous adhesive 103 can utilize usual way manufacture.
The thickness of membranaceous adhesive 103 is not particularly limited, but more than preferably 5 μm, more excellent Elect more than 15 μm as.If less than 5 μm, then producing and the semiconductor wafer of warpage occur or partly leads The position that body chip is the most bonding, bond area can become unstable.It addition, membranaceous adhesive 103 Thickness be preferably below 100 μm, below more preferably 50 μm.If more than 100 μm, then can Make membranaceous adhesive 103 exceedingly ooze out because of the load of chip stickup, thus pad can be polluted.
The surface roughness (Ra) of membranaceous adhesive 103 is preferably 0.1～5000nm.If being less than 0.1nm, then difficulty on coordinating.On the other hand, if being more than 5000nm, then when chip is pasted Attaching with adherend is likely to decrease.
The resistivity of membranaceous adhesive 103 is the lowest more good, and for example, 9 × 10-2Below Ω m.If 9×10-2Below Ω m, then electric conductivity is good, can tackle small-sized-high-density installation.On the other hand, Resistivity is preferably 1 × 10-6More than Ω m.
The thermal conductivity of membranaceous adhesive 103 is the highest more good, for example, more than 0.5W/m K.If More than 0.5W/m K, then thermal diffusivity is good, can tackle small-sized-high-density installation.On the other hand, If less than 0.5W/m K, then poor radiation, accumulation of heat, it is possible to make electric conductivity deteriorate.
The storage tensile modulus of 120 DEG C of membranaceous adhesive 103 is preferably below 10MPa, more excellent Elect below 5MPa as.If below 10MPa, the then membranaceous adhesive 103 near heat curing temperature Mobility high, easily utilize the heating under pressure to eliminate space.The storage tensile modulus of 120 DEG C is excellent Elect more than 0.01MPa as, more preferably more than 0.05MPa.If more than 0.01MPa, then film Shape adhesive 103 is difficult to ooze out.
The storage tensile modulus of 120 DEG C can utilize following method to measure.
The mensuration of the storage tensile modulus of 120 DEG C
From membranaceous adhesive 103, cut out the strip of vertical 30mm, wide 10mm, thick 400 μm Measure sheet.To measuring sheet, use fixing determination of viscoelasticity device (RSA-II, Rheometric Scientific company system) under conditions of frequency 1Hz, programming rate 10 DEG C/min, measure chuck width Degree 22.6mm, 0 DEG C～the storage tensile modulus of 200 DEG C.
The storage tensile modulus of 120 DEG C can utilize the glass transition temperature of thermoplastic resin, conduction The use level etc. of property particle controls.Such as, by coordinating the thermoplastic resin that glass transition temperature is low Fat, can reduce the storage tensile modulus of 120 DEG C.
Membranaceous adhesive 103 preferably uses with the form of the cutting belt with membranaceous adhesive.
As it is shown in figure 5, the cutting belt 110 with membranaceous adhesive possesses cutting belt 101, Yi Jipei The membranaceous adhesive 103 being placed in cutting belt 101.Cutting belt 101 possesses base material 111 and is configured at Adhesive phase 112 on base material 111.Membranaceous adhesive 103 is configured on adhesive phase 112.
As shown in Figure 6, the cutting belt 110 with membranaceous adhesive can also be only (partly to lead at workpiece Body wafer 104 etc.) attach the composition being formed in part with membranaceous adhesive 103.
Explanation about base material 111 is identical with the explanation about base material 1, therefore omits.About adhesive The explanation of layer 112 is identical with the explanation about adhesive phase 112, therefore omits.
Under conditions of exfoliation temperature 25 DEG C, peeling rate 300mm/min, by membranaceous adhesive 103 Peeling force when cutting belt 101 is peeled off is preferably 0.01～3.00N/20mm.If being less than 0.01N/20mm, then likely produce chip during cutting and disperse.On the other hand, if being more than 3.00N/20mm, then have pickup and become the trend of difficulty.
The manufacture method of semiconductor device is illustrated.
As it is shown in fig. 7, the cutting belt 110 with membranaceous adhesive is crimped on semiconductor wafer 104. As semiconductor wafer 104, silicon wafer, silicon carbide wafer, compound semiconductor wafer can be enumerated Deng.As compound semiconductor wafer, gallium nitride wafer etc. can be enumerated.
As compression bonding method, such as, can enumerate the method that press tools such as utilizing crimping roller carries out pressing Deng.
Crimping temperature (attaching temperature) is preferably more than 35 DEG C, more preferably more than 37 DEG C.Preferably press The upper limit of jointing temp is low, preferably less than 50 DEG C, more preferably less than 45 DEG C.By entering at low temperatures Row crimping, is possible to prevent the heat affecting to semiconductor wafer 104, such that it is able to suppression semiconductor wafer The warpage of 104.
It addition, pressure is preferably 1 × 105Pa～1 × 107Pa, more preferably 2 × 105Pa～8 × 106Pa。
Then, as shown in Figure 8, the cutting of semiconductor wafer 104 is carried out.That is, by semiconductor wafer 104 It is cut into given size and singualtion, cuts out semiconductor chip 105.Cutting can be entered according to well-established law OK.It addition, in this operation, such as can use and be cut into the cutting belt 110 with membranaceous adhesive The cutting mode etc. being referred to as entirely cutting.Limit the most especially as cutter sweep used in this operation Fixed, it is possible to use existing known cutter sweep.Further, since semiconductor wafer 104 is by with film The cutting belt 110 of shape adhesive is gluing fixing, and chip defect or chip therefore can be suppressed to disperse, with Time can also suppress the breakage of semiconductor wafer 104.
In order to by the semiconductor chip 105 in the gluing cutting belt 110 being fixed on membranaceous adhesive Peel off, carry out the pickup of semiconductor chip 105.Method as pickup is not particularly limited, permissible Use existing known various methods.For example, it is possible to enumerate with pin by each semiconductor chip 105 from With membranaceous adhesive cutting belt 110 side jack-up, utilize pick device pickup by the semiconductor of jack-up The method etc. of chip 105.
Here, in the case of adhesive phase 112 is ultraviolet hardening, to this adhesive phase 112 It is picked up after irradiation ultraviolet radiation.Thus, the bonding force of membranaceous adhesive 103 is dropped by adhesive phase 112 Low, the stripping of semiconductor chip 105 becomes easy.As a result, it is possible to do not damage semiconductor chip 105 ground pickups.Exposure intensity, the condition such as irradiation time when ultraviolet irradiates are not particularly limited, As long as setting the most as required.
As it is shown in figure 9, the semiconductor chip 105 picked up is pressed from both sides across membranaceous adhesive 103 gluing solid On adherend 106, obtain the adherend 161 with semiconductor chip.With semiconductor chip Adherend 161 possesses adherend 106, the membranaceous adhesive 103 being configured on adherend 106, Yi Jipei It is placed in the semiconductor chip 105 on membranaceous adhesive 103.
Chip sticking temperature is preferably more than 80 DEG C, more preferably more than 90 DEG C.It addition, chip is pasted Temperature is preferably less than 150 DEG C, more preferably less than 130 DEG C.By being set to less than 150 DEG C, permissible The generation of the warpage after preventing chip from pasting.
It follows that make membranaceous glue by heating under elevated pressure with the adherend 161 of semiconductor chip Stick 103 heat cure, makes semiconductor chip 105 and adherend 106 set.By making film under elevated pressure Shape adhesive 103 heat cure, can eliminate and be present between membranaceous adhesive 103 and adherend 106 Space, such that it is able to guarantee the area that membranaceous adhesive 103 contacts with adherend 106.
As carrying out the method that heats under elevated pressure, such as, can enumerate and be filled with indifferent gas by being configured at The method etc. that the adherend 161 with semiconductor chip in the chamber of body heats.
The pressure of pressured atmosphere is preferably 0.5kg/cm2(4.9×10-2MPa) more than, more preferably 1kg/cm2(9.8×10-2MPa) more than, more preferably 5kg/cm2(4.9×10-1MPa) with On.If 0.5kg/cm2Above, then can easily eliminate and be present in membranaceous adhesive 103 and glued Space between thing 106.The pressure of pressured atmosphere is preferably 20kg/cm2(1.96MPa) below, more It is preferably 18kg/cm2(1.77MPa) below, more preferably 15kg/cm2(1.47MPa) with Under.If 20kg/cm2Hereinafter, then the membranaceous adhesive 103 caused by excessive pressurization can be suppressed Ooze out.
Heating-up temperature when heating under elevated pressure is preferably more than 80 DEG C, more preferably 100 DEG C with On, more preferably more than 120 DEG C, particularly preferably more than 170 DEG C.If more than 80 DEG C, then Membranaceous adhesive 103 can be made the hardness of appropriateness, it is possible to use cure under pressure makes space effectively Disappear.
Heating-up temperature is preferably less than 260 DEG C, more preferably less than 200 DEG C, more preferably 180 DEG C with Under.If less than 260 DEG C, being then possible to prevent the decomposition of the membranaceous adhesive 103 before solidification.
Heat time is preferably more than 0.1 hour, more preferably more than 0.2 hour, further preferably It it is more than 0.5 hour.If more than 0.1 hour, then the effect of pressurization can be obtained fully.Add The heat time is preferably less than 24 hours, more preferably less than 3 hours, more preferably 1 hour Below.
As shown in Figure 10, carry out by the front end of the portion of terminal (inner lead) of adherend 106 with partly lead Electrode pad (not shown) on body chip 105 utilizes the wire bond operation that bonding wire 107 electrically connects.As Bonding wire 107, such as, can use gold thread, aluminum steel or copper cash etc..Temperature when carrying out wire bond is preferably More than 80 DEG C, more preferably more than 120 DEG C, this temperature is preferably less than 250 DEG C, more preferably 175 DEG C Below.It addition, its heat time is several seconds～several minutes (such as 1 second～1 minute).Wiring be It is heated to be under the state in described temperature range, by being applied in combination vibrational energy and the pressurization of ultrasonic wave Crimping can be carried out.
It follows that carry out the sealing process utilizing sealing resin 108 to be sealed by semiconductor chip 105.This Operation is in order to protect the semiconductor chip 105 being equipped on adherend 106, bonding wire 107 and to carry out. This operation is by being carried out by the resin forming sealed with mould.As sealing resin 108, example As used the resin of epoxies.Heating-up temperature during resin seal is preferably more than 165 DEG C, more preferably Being more than 170 DEG C, this heating-up temperature is preferably less than 185 DEG C, more preferably less than 180 DEG C.
As required, it is also possible to sealer is heated further (rear curing process).Thus, so that it may So that the sealing resin 108 solidifying deficiency in sealing process is fully cured.Heating-up temperature can be suitably Set.
Folder is comprised across membranaceous adhesive 103 chip joint on adherend 106 as it has been described above, utilize The operation of semiconductor chip 105 and on adherend 106 chip engage the work of semiconductor chip 105 The method being allowed to the operation of heat cure by being heated under elevated pressure by membranaceous adhesive 103 after sequence, Manufacture semiconductor device.That is, utilize comprise will be provided with membranaceous adhesive 103 and with membranaceous adhesive The chip joint chip of the semiconductor chip 105 of 103 contacts is crimped on the work on adherend 106 Sequence, after chip joint chip is crimped on the operation on adherend 106 by by membranaceous adhesive 103 heat and the method that is allowed to the operation of heat cure under elevated pressure, manufacture semiconductor device.
More specifically, the method comprises: at the membranaceous glue of the cutting belt 110 with membranaceous adhesive On stick 103, the operation of configuring semiconductor wafer 104, cutting are configured on membranaceous adhesive 103 Semiconductor wafer 104 and form the operation of semiconductor chip 105, by semiconductor chip 105 with membranaceous Operation that adhesive 103 picks up together, folder are across membranaceous adhesive 103 chip on adherend 106 Engage the operation of semiconductor chip 105, on adherend 106, chip engages semiconductor chip 105 Operation after be allowed to the operation of heat cure by being heated under elevated pressure by membranaceous adhesive 103.
Above, it is described with the 3rd.
[embodiment]
Hereinafter, use embodiment that first, second and third present invention is described in detail, but the One, second and third present invention is without departing from its purport, is just not limited to below example.Separately Outward, in each example, as long as no recording especially, part is exactly weight basis.
[first and second embodiments of the invention]
The composition used in embodiment is illustrated.
The Aron Tac S-2060 (acrylic acid that Aron Tac S-2060: East Asia synthesis (strain) is made Analog copolymer, Mw:55 ten thousand, glass transition temperature :-22 DEG C)
The Teisan Resin SG that Teisan Resin SG-70L:Nagase ChemteX (strain) makes -70L (acrylic copolymer, Mw:90 ten thousand, glass transition temperature :-13 DEG C)
EOCN-1020-4: the EOCN-1020-4 that Japan's chemical drug (strain) makes (when 25 DEG C is The epoxy resin of solid)
The JER828 (being aqueous epoxy resin when 25 DEG C) that JER828: Mitsubishi Chemical (strain) makes
MEH-7851SS: the bright and MEH-7851SS (phenol aralkyl resin) of chemical conversion company
1400YM: 1400YM (copper powder, spherical, the average particle that Mitsui Metal Co., Ltd.'s mining industry (strain) is made Footpath 4 μm, proportion 8.9)
1300YM: 1300YM (copper powder, spherical, the average particle that Mitsui Metal Co., Ltd.'s mining industry (strain) is made Footpath 3 μm, proportion 8.9)
ES-6000 that ES-6000:Potters Ballotini (strain) makes (silver coated glass bead, spherical, Average grain diameter 6 μm, proportion 3.9～4.0)
AUP-1000: (bronze is last, spherical, average for the AUP-1000 that big rugged industry (strain) is made Particle diameter 1 μm, proportion 19.3)
1200YP: 1200YP that Mitsui Metal Co., Ltd.'s mining industry (strain) is made (flake copper, average grain diameter 3.5 μm, Aspect ratio: 10, proportion 8.9)
1050YP: 1050YP that Mitsui Metal Co., Ltd.'s mining industry (strain) is made (flake copper, average grain diameter 0.9 μm, Aspect ratio: 4, proportion 8.9)
1400YP: 1400YP that Mitsui Metal Co., Ltd.'s mining industry (strain) is made (flake copper, average grain diameter 7.0 μm, Aspect ratio: 25, proportion 8.9)
SPQ01: SPQ01 that Mitsui Metal Co., Ltd.'s mining industry (strain) is made (silver powder, spherical, average grain diameter 0.1 μm, Proportion 10.5)
EHD: EHD that Mitsui Metal Co., Ltd.'s mining industry (strain) is made (silver powder, spherical, average grain diameter 0.7 μm, Proportion 10.5)
[membranaceous adhesive and the making of cutting belt with membranaceous adhesive]
(embodiment and comparative example)
According to the match ratio described in table 1～2, by each composition described in table 1～2 and solvent (first and second Ketone) add mixing and blending machine (KEYENCE HM-500) stirred tank in, to stir mould Formula stirring, mixing 3 minutes.The varnish of gained utilizes die coating machine coat the demoulding and processes film (Mitsubishi The MRA50 that resin (strain) is made) upper after, be allowed to dry, produce membranaceous adhesive.
Membranaceous adhesive by gained is cut into the circle of diameter 230mm, is pasted onto cutting at 25 DEG C On the adhesive phase of band (P2130G that day east electrician (strain) makes), produce with membranaceous gluing The cutting belt of agent.
[making of minute surface silicon wafer]
Use wafer mill back of the body machine (DFG-8560 of (strain) DISCO), be ground to silicon wafer (letter More chemical industry (strain) system, thick 0.6mm) thickness be 0.05mm, produce minute surface silicon wafer.
[evaluation]
Use the membranaceous adhesive of gained, carry out with cutting belt, the minute surface silicon wafer of membranaceous adhesive Following evaluation.The results are shown in table 1～2.
[cementability evaluation]
Use chip mounter (MA-3000III that day east essence machine (strain) makes), to attach speed 10mm/min, attaching temperature 40 DEG C are pasted on the membranaceous adhesive of the cutting belt with membranaceous adhesive Close minute surface silicon wafer.
The material cutting machine (DFD-6361 of (strain) DISCO) utilizing laminating to obtain is cut Cutting (singualtion) is 10mm × 10mm, obtains monolithic.((strain) is new to use chip engagement machine The SPA-300 in river), with 120 DEG C, 0.1MPa, 1 second on lead frame chip paste monolithic (bag Containing chip and the monolithic of membranaceous adhesive).Scanning electron microscope is utilized to observe after chip is pasted The side of monolithic, if very close to each other between monolithic and lead frame, is then judged to "None", if between having Gap, then be judged to " having ".
[oozing out evaluation]
Use chip mounter (MA-3000III that day east essence machine (strain) makes), to attach speed 10mm/min, attaching temperature 40 DEG C are pasted on the membranaceous adhesive of the cutting belt with membranaceous adhesive Close minute surface silicon wafer.
The material cutting machine (DFD-6361 of (strain) DISCO) utilizing laminating to obtain is cut Cutting (singualtion) is 10mm × 10mm, obtains monolithic.((strain) is new to use chip engagement machine The SPA-300 in river), with 120 DEG C, 0.4MPa, 1 second on lead frame chip paste monolithic (bag Containing chip and the monolithic of membranaceous adhesive).Use light microscope viewed from above after chip is pasted Monolithic, determines the end face from chip and oozes out the distance (oozing out distance) of membranaceous adhesive.
[membranaceous adhesive measures with the peeling force of cutting interband]
On the membranaceous adhesive of the cutting belt with membranaceous adhesive, poly-for keeping purpose to fit After ester adhesive tape (BT-315 that day east electrician (strain) makes), cut with 100mm × 100mm width, Produce sample.To this sample, utilize T-shaped with peeling rate 300mm/min, exfoliation temperature 25 DEG C Peel off and peel off membranaceous adhesive from cutting belt, determine peeling force.
[mensuration of specific insulation]
To membranaceous adhesive, use resistrivity meter (the Loresta MP that Mitsubishi Chemical's (strain) makes MCP-T350), four probe method based on JIS K 7194 is utilized to carry out the mensuration of specific insulation.
[size distribution of electroconductive particle and the mensuration of average grain diameter]
The membranaceous adhesive of embodiment 2, embodiment 6, comparative example 5 and comparative example 6 is put into crucible, Apply heat-flash and make membranaceous adhesive be ashed.The ash content of gained is scattered in pure water and carries out 10 points Clock ultrasonic wave processes, and (Beckman Kurt is public to use laser diffraction and scattering formula particle size distribution device Department's system, " LS 13 320 "；Damp process) obtain size distribution (volume reference) and average grain diameter. And, the composition as membranaceous adhesive is organic principle in addition to electroconductive particle, owing to utilizing Above-mentioned heat-flash processes substantially to be burnt all of organic principle, is therefore regarded as by the ash content of gained Electroconductive particle and be determined.
[synthetic determination]
The situation meeting following full terms is judged to zero, the situation being unsatisfactory for any one is sentenced Be set to ×.
Condition (1): the result of determination of cementability evaluation is "None".
Condition (2): oozing out the distance of oozing out measured in evaluation is below 100 μm.
Condition (3): membranaceous adhesive with cutting interband peeling force measure measurement result be 0.01～ 3.00N/20mm。
Condition (4): the specific insulation of membranaceous adhesive is 1 × 10-6More than Ω m and 9 × 10-2Ω Below m.
[table 1]
[table 1]
[table 2]
[table 2]
Employ the embodiment 1 of the membranaceous adhesive containing the platy particle that aspect ratio is more than 5, implement Example 3～5, embodiment 7 can obtain the electric conductivity of excellence.On the other hand, employ containing in length and breadth Poorly conductive in the comparative example 4 of the membranaceous adhesive comparing the platy particle being 4.
Employ in the embodiment 2 of the membranaceous adhesive containing 2 kinds of spherical particles, embodiment 6, it is possible to To obtain excellent electric conductivity.On the other hand, the membranaceous adhesive containing a kind of spherical particle is employed Comparative example 1～3, in comparative example 5～6, poorly conductive.
And, the ash content to the membranaceous adhesive of embodiment 2, embodiment 6, comparative example 5 and comparative example 6, Determine size distribution and average grain diameter.This measurement result is and the average grain diameter according to electroconductive particle The roughly the same result of value calculated.
Above, first and second embodiments of the invention are illustrated.
[the 3rd embodiments of the invention]
The composition used in embodiment is illustrated.
The Teisan Resin SG that Teisan Resin SG-70L:Nagase ChemteX (strain) makes -70L (carboxylic acrylic copolymer, Mw:90 ten thousand, acid number: 5mgKOH/g, glass Glass transition temperature :-13 DEG C)
EOCN-1020-4: the EOCN-1020-4 that Japan's chemical drug (strain) makes (when 25 DEG C is The epoxy resin of solid)
The JER828 (being aqueous epoxy resin when 25 DEG C) that JER828: Mitsubishi Chemical (strain) makes
MEH-7851SS: the bright and MEH-7851SS (phenol aralkyl resin) of chemical conversion company
1400YM: 1400YM (copper powder, spherical, the average particle that Mitsui Metal Co., Ltd.'s mining industry (strain) is made Footpath 4 μm, proportion 8.9)
1200YP: 1200YP that Mitsui Metal Co., Ltd.'s mining industry (strain) is made (flake copper, average grain diameter 3.5 μm, Aspect ratio: 10, proportion 8.9)
EHD: EHD that Mitsui Metal Co., Ltd.'s mining industry (strain) is made (silver powder, spherical, average grain diameter 0.7 μm, Proportion 10.5)
[membranaceous adhesive and the making of cutting belt with membranaceous adhesive]
(embodiment 8～10 and comparative example 7～9)
According to the match ratio described in table 3～table 4, by each composition described in table 3～table 4 and solvent (MEK) adds in the stirred tank of mixing and blending machine (KEYENCE HM-500), with Stir mode stirring, mixing 3 minutes.The varnish of gained utilizes die coating machine coat the demoulding and processes film After (MRA50 that Mitsubishi's resin (strain) is made) is upper, it is allowed to dry, produces membranaceous adhesive.
Membranaceous adhesive by gained is cut into the circle of diameter 230mm, is pasted onto cutting at 25 DEG C On the adhesive phase of band (P2130G that day east electrician (strain) makes), produce with membranaceous gluing The cutting belt of agent.
[evaluation]
Membranaceous adhesive to gained, the cutting belt with membranaceous adhesive, carried out following evaluation. The results are shown in table 3～table 4.
[bond area]
(evaluation method of embodiment 8～10)
Use chip mounter (MA-3000III that day east essence machine (strain) makes), to attach speed 10mm/min, attaching temperature 40 DEG C are pasted on the membranaceous adhesive of the cutting belt with membranaceous adhesive Close minute surface silicon wafer.
Minute surface silicon wafer cutting machine ((strain) that will be configured in the cutting belt with membranaceous adhesive The DFD-6361 of DISCO) cutting (singualtion) be 10mm × 10mm, obtain monolithic. Use the chip engagement machine SPA-300 of ((strain) new river), with 120 DEG C, 0.1MPa, 1 second folder Monolithic is pasted across membranaceous adhesive chip on lead frame.Cure under pressure stove is used after chip is pasted ((strain) sandy fields where reeds grow makes made MODEL AC), carries out cure under pressure under the conditions shown in Table 3. After solidification, ultrasonic microscope is used to observe the bond area that membranaceous adhesive is gluing with lead frame.Will Bond area be more than 95% situation be judged to zero, the situation less than 95% is judged to ×.And, For bond area, the value of percentage is the biggest, then be present between membranaceous adhesive and lead frame Space is the fewest.
(evaluation method of comparative example 7～9)
Except replacing cure under pressure stove, and use drying machine (STC-120H of (strain) Espec) Carry out under the conditions shown in Table 4 being not pressurized beyond solidification this point, utilize identical with embodiment 8～10 Method have rated bond area.
[table 3]
[table 3]
Cures under pressure)
[table 4]
[table 4]
Solidify under atmospheric pressure)
Above, the 3rd embodiments of the invention are illustrated.
The explanation of symbol
1 base material,
2 adhesive phases,
3 membranaceous adhesive,
4 semiconductor wafers,
5 semiconductor chips,
6 adherends,
7 bonding wires,
8 sealing resins,
10 with the cutting belt of membranaceous adhesive,
11 cutting belt,
110 with the cutting belt of membranaceous adhesive,
101 cutting belt,
111 base materials,
112 adhesive phases,
103 membranaceous adhesive,
104 semiconductor wafers,
105 semiconductor chips,
106 adherends,
161 with the adherend of semiconductor chip,
107 bonding wires,
108 sealing resins

Claims (10)

1. a membranaceous adhesive, it contains electroconductive particle,
Described electroconductive particle be in gold particle, silver particles, copper particle and coating particles at least 1 kind,
Described coating particles possesses core particle and is coated with the coating film of described core particle,
Described coating film contains at least a kind in gold, silver and copper,
Described electroconductive particle contains the platy particle that aspect ratio is more than 5,
The content of the described platy particle in described electroconductive particle 100 weight % be 5 weight %～ 100 weight %.
Membranaceous adhesive the most according to claim 1, wherein,
The content of the described electroconductive particle in described membranaceous adhesive is 30 weight %～95 weights Amount %.
Membranaceous adhesive the most according to claim 1 and 2, wherein,
Specific insulation is 1 × 10-6More than Ω m and 9 × 10-2Below Ω m.
4., with a cutting belt for membranaceous adhesive, it possesses cutting belt and is laminated in described cutting Membranaceous adhesive according to any one of claims 1 to 3 on band.
5. a manufacture method for semiconductor device, it includes using any one of claim 1～3 Described membranaceous adhesive chip on adherend pastes the operation of semiconductor chip.
6. a membranaceous adhesive, it contains electroconductive particle,
Described electroconductive particle be in gold particle, silver particles, copper particle and coating particles at least 1 kind,
Described coating particles possesses core particle and is coated with the coating film of described core particle,
Described coating film contains at least a kind in gold, silver and copper,
Described electroconductive particle contains spherical spherical particle,
In the size distribution of described spherical particle, there is the peak value of more than 2,
Peak A is there is, at 3 μm～the particle diameter of 15 μm in the particle size range of 0.2 μm～0.8 μm Scope exists peak value B,
The particle diameter of described peak value B is 5～15 with the ratio of the particle diameter of described peak A.
Membranaceous adhesive the most according to claim 6, wherein,
The content of the described electroconductive particle in described membranaceous adhesive is 30 weight %～95 weights Amount %.
8., according to the membranaceous adhesive described in claim 6 or 7, its specific insulation is 1 × 10-6Ω· More than m and 9 × 10-2Below Ω m.
9., with a cutting belt for membranaceous adhesive, it possesses cutting belt and is laminated in described cutting The membranaceous adhesive according to any one of claim 6～8 on band.
10. a manufacture method for semiconductor device, it includes using any one of claim 6～8 Described membranaceous adhesive chip on adherend pastes the operation of semiconductor chip.
CN201480072327.8A 2014-01-08 2014-12-22 Film-like adhesive, dicing tape with film-like adhesive, method for manufacturing semiconductor device, and semiconductor device Pending CN105899629A (en)

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JP2014-001516 2014-01-08
PCT/JP2014/083896 WO2015104986A1 (en) 2014-01-08 2014-12-22 Film-like adhesive, dicing tape with film-like adhesive, method for manufacturing semiconductor device, and semiconductor device

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JP4635412B2 (en) * 2003-07-22 2011-02-23 住友ベークライト株式会社 Conductive adhesive film and semiconductor device using the same
JP6033734B2 (en) * 2013-04-30 2016-11-30 日東電工株式会社 Film adhesive, dicing tape integrated film adhesive, and method for manufacturing semiconductor device

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