CN105505244A - Chip bonding film, dicing chip bonding film, and semiconductor apparatus - Google Patents

Chip bonding film, dicing chip bonding film, and semiconductor apparatus Download PDF

Info

Publication number
CN105505244A
CN105505244A CN201510901642.3A CN201510901642A CN105505244A CN 105505244 A CN105505244 A CN 105505244A CN 201510901642 A CN201510901642 A CN 201510901642A CN 105505244 A CN105505244 A CN 105505244A
Authority
CN
China
Prior art keywords
bonding film
die bonding
weight
dicing
film
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
CN201510901642.3A
Other languages
Chinese (zh)
Inventor
大西谦司
盛田美希
宍户雄一郎
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
Original Assignee
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
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of CN105505244A publication Critical patent/CN105505244A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27—Manufacturing methods
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C09J2433/006—Presence of (meth)acrylic polymer in the substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/156—Material
    • H01L2924/157—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
    • H01L2924/15738—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
    • H01L2924/15747—Copper [Cu] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/156—Material
    • H01L2924/15786—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
    • H01L2924/15788—Glasses, e.g. amorphous oxides, nitrides or fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Die Bonding (AREA)
  • Dicing (AREA)

Abstract

The invention relates to a chip bonding film, a dicing chip bonding film, and a semiconductor apparatus. The chip bonding film, capable of reducing generations of points at a boundary of the chip bonding film and an adhered body even when exposed to a high temperature for a long time, is provided. The chip bonding film contains a thermosetting acrylic copolymer having a nitrile group and a curing agent. A thermal discharge is 10mJ/mg and less by using a differential scanning calorimeter at a heating rate of 10 DEG C minutes from 25 DEG C to 300 DEG C.

Description

Die bonding film, dicing/die bonding film and semiconductor device
The divisional application that the application is the applying date is on August 3rd, 2012, Chinese application number is the Chinese patent application of 201210275227.8.
Technical field
The present invention relates to by such as semi-conductor chip etc. semiconductor element is gluing be fixed on the adherend such as substrate or lead frame time use die bonding film.In addition, the present invention relates to this die bonding film and the dicing/die bonding film cutting pellicular cascade.In addition, the present invention relates to the semiconductor device using this die bonding film or this dicing/die bonding film to manufacture.
Background technology
In the past, in the manufacturing processed of semiconductor device, lead frame and electrode member adopt silver slurry during set semi-conductor chip.Described set process, by being coated with pulpous state tackiness agent on the chip bonding pad etc. of lead frame, being carried semi-conductor chip thereon and pulpous state adhesive layer is solidified and carry out.
But pulpous state tackiness agent produces large deviation due to its viscosity behavior or deterioration etc. in glue spread or coating shape etc.As a result, the pulpous state Adhesive thickness of formation is uneven, and therefore the set intensity of semi-conductor chip lacks reliability.That is, the set intensity when glue spread of pulpous state tackiness agent is not enough between semi-conductor chip and electrode member reduces, and in follow-up wire bond operation, semi-conductor chip is peeled off.On the other hand, when the glue spread of pulpous state tackiness agent is too much, pulpous state tackiness agent curtain coating to semi-conductor chip produces bad characteristic, thus yield rate and reliability decrease.Problem in such set process, the maximization with semi-conductor chip becomes remarkable especially.Therefore, need the control of the glue spread of carrying out pulpous state tackiness agent continually, thus bring problem to workability or productivity.
In the painting process of this pulpous state tackiness agent, there is the method be applied to respectively by pulpous state tackiness agent on the chip of lead frame or formation.But in the method, pulpous state adhesive layer is difficult to homogenizing, the coating of pulpous state tackiness agent needs special device with long-time in addition.Therefore, gluing maintenance semi-conductor chip in cutting action is proposed and the cutting film (such as, referenced patent document 1) also providing required chip set to stick with glue oxidant layer in installation procedure.
This cutting film is, on support base material, the mode that can peel off is provided with adhesive layer, after semiconductor wafer being cut under the maintenance of this adhesive layer, support base material stretched and the chip of formation is peeled off together with adhesive layer and it is reclaimed respectively, being then affixed on the adherends such as lead frame by this adhesive layer.Now, usually between adhesive layer and adherend, there is space.In the past, by the heat in the sealing process that utilizes sealing resin to carry out or pressure, space was disappeared.
On the other hand, manufacturing the stacked and semiconductor device that obtains of multiple semi-conductor chip multistage in recent years, there is the wire bond operation of carrying out wire bond to semi-conductor chip, tendency that the time that the operation etc. of die bonding film thermofixation is spent increases.And, when being exposed under high temperature for a long time, there is the tendency do not disappeared in sealing process at the bubble (space) of the boundary of die bonding film and adherend.This space can cause semi-conductor chip to peel off from adherend, thus there is the problem lacking gluing reliability.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 60-57642 publication
Summary of the invention
The present invention foundes in view of foregoing problems, even if its object is to provide the generation in the boundary space also can reducing die bonding film and adherend when at high temperature carrying out long time treatment, and the semiconductor device that can suppress the die bonding film of the stripping in reflow soldering operation, dicing/die bonding film and use this die bonding film or this dicing/die bonding film to manufacture.
Present inventor, in order to solve aforesaid problem, is studied with the dicing/die bonding film of cutting pellicular cascade die bonding film and this die bonding film.Found that, at high temperature during process chip bonding film, because heat reactive resin composition contained in die bonding film reacts tempestuously, therefore do not disappear in sealing process at the bubble (space) of the boundary of die bonding film and adherend.And, by adopting following formation, suppressing the reaction of heat reactive resin composition contained in die bonding film, can in sealing process, make space disappear thus, and complete the present invention.
That is, die bonding film of the present invention, is characterized in that, containing nitrile group-containing thermoset acrylics analog copolymer and solidifying agent, use differential calorimeter, thermal discharge when measuring from 25 DEG C to 300 DEG C with the heat-up rate of 10 DEG C/min is below 10mJ/mg.
According to aforementioned formation, use differential calorimeter, thermal discharge when measuring from 25 DEG C to 300 DEG C with the heat-up rate of 10 DEG C/min is below 10mJ/mg, thus the reaction of described thermosetting resin component and described solidifying agent is suppressed.Therefore, the boundary of die bonding film and adherend can be suppressed to produce space.As a result, even if when at high temperature carrying out process for a long time, the generation in the boundary space of die bonding film and adherend also can be reduced.In addition, according to aforementioned formation, due to containing itrile group, therefore cohesive force rises.As a result, the stripping in reflow soldering operation can be suppressed.That is, according to aforementioned formation, the suppression of peeling off in the suppression in space and reflow soldering operation can be realized simultaneously.
In aforementioned formation, preferably: with 175 DEG C of thermofixations after 5 hours for benchmark, the temperature of weightless 5 % by weight is more than 280 DEG C, is less than 1 % by weight at the water-intake rate of 175 DEG C of thermofixations after 5 hours.By realize with 175 DEG C of thermofixations after 5 hours for the temperature of benchmark weightless 5 % by weight is more than 280 DEG C, and be less than 1 % by weight at the water-intake rate of 175 DEG C of thermofixations after 5 hours, can prevent in reflow soldering operation with the stripping that described space is starting point.In addition, the temperature of weightless 5 % by weight refers to: by the die bonding film of 175 DEG C of thermofixations after 5 hours with the heating of the heat-up rate (such as 10 DEG C/min) of regulation, the weight of die bonding film reduces temperature (TGA when 5%; TGA method).In addition, reflow soldering operation refers to, after assembled semiconductor encapsulation, use solder attach it to printed wiring board etc. upper time the operation of process, be normally heated to the operation of about 260 DEG C.
In aforementioned formation, preferably: the stretching store elastic modulus at after 5 hours 260 DEG C of 175 DEG C of thermofixations is more than 0.5MPa.When stretching store elastic modulus at after 5 hours 260 DEG C of 175 DEG C of thermofixations is more than 0.5MPa, can prevent further in reflow soldering operation with the stripping that described space is starting point.
In aforementioned formation, preferably: set the weight of described nitrile group-containing thermoset acrylics analog copolymer as the weight of x, described solidifying agent be y time, weight ratio (x/y) is more than 2 and less than 20.When described weight ratio (x/y) is more than 2, described thermal discharge is easily made to be below 10mJ/mg.On the other hand, when described weight ratio (x/y) is less than 20, easily give the cohesive force that opposing is peeled off when carrying out reflow soldering operation.
In aforementioned formation, preferably: the weight-average molecular weight of described nitrile group-containing thermoset acrylics analog copolymer is more than 500,000.When the weight-average molecular weight of described nitrile group-containing thermoset acrylics analog copolymer is more than 500,000, easily give the cohesive force that opposing is peeled off further when carrying out reflow soldering operation.
In aforementioned formation, preferably: described nitrile group-containing thermoset acrylics analog copolymer contains epoxy group(ing), and oxirane value is more than 0.1eq/kg and below 1eq/kg.When described oxirane value is more than 0.1eq/kg, even if the sufficient Young's modulus under high temperature also can be obtained after thermofixation.On the other hand, when described oxirane value is below 1eq/kg, the reaction with solidifying agent can be suppressed further.
In aforementioned formation, preferably: described solidifying agent has phenolic hydroxyl group.When described solidifying agent has phenolic hydroxyl group, can by improving cohesive force further with the reaction of epoxy group(ing).
In addition, in order to solve aforementioned problems, the feature of dicing/die bonding film of the present invention is, aforesaid die bonding film is layered on cutting film.
In aforementioned formation, preferably: the stretching store elastic modulus at 25 DEG C before the thermofixation of described die bonding film is more than 1MPa and below 5GPa.When stretching store elastic modulus at 25 DEG C before the thermofixation of described die bonding film is more than 1MPa, with the peeling force appropriateness of cutting film, pick can be improved.On the other hand, when the stretching store elastic modulus at 25 DEG C before the thermofixation of described die bonding film is below 5GPa, operability is excellent.
In addition, in order to solve aforementioned problems, the feature of semiconductor device of the present invention is, uses aforesaid die bonding film or dicing/die bonding film manufacture.
Accompanying drawing explanation
Fig. 1 is the schematic sectional view of the dicing/die bonding film representing an embodiment of the invention.
Fig. 2 is the schematic sectional view of the dicing/die bonding film representing another embodiment of the present invention.
Fig. 3 is the schematic sectional view of the example represented by the adhesive layer mounting semiconductor chip in the dicing/die bonding film shown in Fig. 1.
Fig. 4 is the schematic sectional view of the example represented by the three-dimensional mounting semiconductor chip of the adhesive layer in the dicing/die bonding film shown in Fig. 1.
Fig. 5 represents to use the dicing/die bonding film shown in Fig. 1, utilizes adhesive layer three-dimensional to install the schematic sectional view of the example of two semi-conductor chips across pad.
Fig. 6 represents the figure being measured the typical differential calorimetric curve obtained by means of differential scanning calorimetry.
Label declaration
1 base material
2 binder layers
3,3 ' die bonding film (thermosetting die bonding film)
4 semiconductor wafers
5 semi-conductor chips
6 adherends
7 bonding wires
8 sealing resins
10,12 dicing/die bonding films
11 cutting films
13 die bonding films (thermosetting die bonding film)
15 semi-conductor chips
21 die bonding films (thermosetting die bonding film)
Embodiment
(dicing/die bonding film)
Dicing/die bonding film below for an embodiment of the invention is described.Fig. 1 is the schematic sectional view of the dicing/die bonding film representing an embodiment of the invention.Fig. 2 is the schematic sectional view of the dicing/die bonding film representing another embodiment of the present invention.
As shown in Figure 1, dicing/die bonding film 10 has the formation being laminated with die bonding film 3 on cutting film 11.Cutting film 11 is consisted of stacked binder layer 2 on base material 1, and die bonding film 3 is arranged on this binder layer 2.In addition, in the present invention, also dicing/die bonding film 12 as shown in Figure 2 only can be formed with the formation of die bonding film 3 ' like this at the workpiece adhesive portion 2a of binder layer 2.
Die bonding film 3,3 ' only comprises adhesive layer individual layer, and containing nitrile group-containing thermoset acrylics analog copolymer and solidifying agent.In addition, in present embodiment, the situation only comprising adhesive layer individual layer for die bonding film 3,3 ' is described, but, in the present invention, the stepped construction of die bonding film 3,3 ' is not particularly limited, such as, and also can for being formed with the structures such as the multilayered structure of adhesive layer in the one or two sides of core.As described core, can enumerate: the resin substrates that film (such as, Kapton, polyester film, pet film, PEN film, polycarbonate film etc.), glass fibre or plastics non-woven fibre strengthen, silicon substrate or glass substrate etc.
About die bonding film 3,3 ', use differential calorimeter, thermal discharge when measuring from 25 DEG C to 300 DEG C with the heat-up rate of 10 DEG C/min is below 10mJ/mg.Described thermal discharge is preferably below 8mJ/mg, more preferably below 5mJ/mg.In addition, described thermal discharge is more little more preferred, such as, is more than 0.001mJ/mg.Because described thermal discharge is below 10mJ/mg, therefore can suppress die bonding film 3,3 ' and the boundary of adherend 6 (with reference to figure 3) produce space.As a result, even if when at high temperature carrying out long time treatment, die bonding film 3,3 ' and the generation in boundary space of adherend also can be reduced.As the method described thermal discharge being controlled to below 10mJ/mg, can enumerate: make the method that thermoset acrylics analog copolymer and solidifying agent react, the method etc. not using in fact curing catalyst.
About die bonding film 3,3 ', with 175 DEG C of thermofixations after 5 hours for benchmark, the temperature of weightless 5 % by weight is preferably more than 280 DEG C, more preferably more than 290 DEG C, preferably more than 300 DEG C further.Described weightless temperature is more high more preferred, such as, is less than 450 DEG C.
In addition, about die bonding film 3,3 ', be preferably less than 1 % by weight at the water-intake rate of 175 DEG C of thermofixations after 5 hours, more preferably less than 0.9 % by weight, further preferably less than 0.8 % by weight.Described water-intake rate is the smaller the better, such as, is more than 0.05 % by weight.The method that described water-intake rate can be recorded by embodiment obtains.
Die bonding film 3,3 ', by realize with 175 DEG C of thermofixations after 5 hours for the temperature of benchmark weightless 5 % by weight is more than 280 DEG C, and be less than 1 % by weight at the water-intake rate of 175 DEG C of thermofixations after 5 hours, can prevent thus in reflow soldering operation with the stripping that described space is starting point.
About die bonding film 3,3 ', the stretching store elastic modulus at after 5 hours 260 DEG C of 175 DEG C of thermofixations is preferably more than 0.5MPa, more preferably more than 0.55MPa and below 3000MPa, further preferably more than 0.6MPa and below 2000MPa.When stretching store elastic modulus at after 5 hours 260 DEG C of 175 DEG C of thermofixations is more than 0.5MPa, can prevent further in reflow soldering operation with the stripping that described space is starting point.
About die bonding film 3,3 ', if when the weight of described nitrile group-containing thermoset acrylics analog copolymer is x, the weight of described solidifying agent is y, weight ratio (x/y) is preferably more than 2 and less than 20, and more preferably more than 2.3 and less than 15.6, further preferably more than 3 and less than 11.5.When described weight ratio (x/y) is more than 2, described thermal discharge is easily below 10mJ/mg.On the other hand, when described weight ratio (x/y) is less than 20, easily give the cohesive force that opposing is peeled off when carrying out reflow soldering operation.
Described nitrile group-containing thermoset acrylics analog copolymer, preferable weight-average molecular weight is more than 500,000, more preferably more than 800,000 and less than 2,000,000.When the weight-average molecular weight of described nitrile group-containing thermoset acrylics analog copolymer is more than 500,000, easily give the cohesive force that opposing is peeled off further when carrying out reflow soldering operation.
Described nitrile group-containing thermoset acrylics analog copolymer, preferably containing epoxy group(ing), and oxirane value is more than 0.1eq/kg and below 1eq/kg, more preferably more than 0.15eq/kg and below 0.8eq/kg, further preferably more than 0.2eq/kg and below 0.6eq/kg.When described oxirane value is more than 0.1eq/kg, even if the sufficient Young's modulus under high temperature also can be obtained after thermofixation.On the other hand, when described oxirane value is below 1eq/kg, the reaction with solidifying agent can be suppressed further.
In addition, the glass transition point (Tg) of described nitrile group-containing thermoset acrylics analog copolymer, as long as can in die bonding film 3, the tackiness obtaining appropriateness between 3 ' and adherend (such as wafer), then be not particularly limited, preferably more than-15 DEG C and less than 40 DEG C, more preferably more than-10 DEG C and less than 35 DEG C.This is because: by being set as more than-15 DEG C, can make the tackiness of semiconductor wafer abundant.In addition, this is because: by being set as less than 40 DEG C, can suppress to be clamminess, raising operability.In addition, glass transition point can be obtained by the method described in embodiment.
As described nitrile group-containing thermoset acrylics base polymer, be not particularly limited, can enumerate: in the polymkeric substance (multipolymer) of composition, add the monomer with heat-curable functional group and the polymkeric substance obtained having the acrylate of straight or branched alkyl or methacrylic ester using one or more.
As described alkyl, can enumerate such as: methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, amyl group, isopentyl, hexyl, heptyl, cyclohexyl, 2-ethylhexyl, octyl group, iso-octyl, nonyl, different nonyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, octadecyl or eicosyl etc.
As the manufacture method of described nitrile group-containing thermoset acrylics base polymer, be not particularly limited, can enumerate such as: nitrile group-containing monomer and acrylic monomer are carried out the method for copolymerization with the monomer with heat-curable functional group.In addition, also can enumerate: the method for adding the monomer with heat-curable functional group in the multipolymer of nitrile group-containing monomer and acrylic polymers.In addition, as other method, can enumerate: by after acrylic monomer and the monomer copolymerization with the first functional group, make to have and can carry out condensation or addition reaction with the described functional group of the first functional group reactions and the compound of itrile group under the situation keeping itrile group, then add the method with heat-curable functional group.
In addition, described nitrile group-containing thermoset acrylics base polymer can for using itrile group, heat-curable functional group and one or more there is the acrylate of straight or branched alkyl or the methacrylic ester polymkeric substance (multipolymer) as composition.Now, as the manufacture method of described nitrile group-containing thermoset acrylics base polymer, be not particularly limited, can enumerate such as: by the method for nitrile group-containing monomer, the monomer with heat-curable functional group and acrylic monomer copolymerization.
In addition, as the manufacture method of described nitrile group-containing thermoset acrylics base polymer, can enumerate:
(A) after the monomer copolymerization that will there is the monomer of heat-curable functional group, acrylic monomer and there is the first functional group, make to have under the situation keeping itrile group can with the method for the described functional group of the first functional group reactions and the compound condensation of itrile group or addition;
(B) after the monomer copolymerization that will there is the monomer of itrile group, acrylic monomer and there is the second functional group, make to have under the situation keeping heat-curable functional group can with the method for the described functional group of the second functional group reactions and the compound condensation of heat-curable functional group or addition;
(C) after by acrylic monomer, the monomer with the second functional group and monomer (being total to) polymerization with the first functional group, make to have under the situation keeping heat-curable functional group can with the described functional group of the second functional group reactions and the compound condensation of heat-curable functional group or addition and make to have under the situation keeping itrile group can with the method for the described functional group of the first functional group reactions and the compound condensation of itrile group or addition.
As described nitrile group-containing monomer, (methyl) vinyl cyanide, cyano-styrene etc. can be enumerated.
As the described monomer with heat-curable functional group, can suitably use such as: having glycidyl and have can the monomer of ethylenic unsaturated bond of copolymerization, can enumerate such as: glycidyl acrylate, glycidyl methacrylate etc. are containing glycidyl monomer.In addition, as described other example with the monomer of heat-curable functional group, maleimide acrylate can be enumerated.
Form the mixture ratio of the monomer of described nitrile group-containing thermoset acrylics base polymer, preferably consider second-order transition temperature, oxirane value regulates.Especially, as the content described in described nitrile group-containing thermoset acrylics base polymer with the monomer of heat-curable functional group, from the viewpoint of second-order transition temperature, oxirane value, preferably 1 ~ 20 % by mole, more preferably 1 ~ 15 % by mole, preferably 1 ~ 10 % by mole further.The polymerization process of described nitrile group-containing thermoset acrylics base polymer is not particularly limited, and can adopt the existing known methods such as such as solution polymerization process, mass polymerization, suspension polymerization, emulsion polymerization.
As other monomer forming described nitrile group-containing thermoset acrylics base polymer, be not particularly limited, can enumerate such as: carboxyl group-containing monomer, as vinylformic acid, methacrylic acid, carboxy ethyl acrylate, carboxypentyl acrylate, methylene-succinic acid, toxilic acid, fumaric acid or β-crotonic acid etc.; Anhydride monomers, as maleic anhydride or itaconic anhydride etc.; Hydroxyl monomer, as (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-4-hydroxybutyl, the own ester of (methyl) vinylformic acid-6-hydroxyl, (methyl) vinylformic acid-8-hydroxyl monooctyl ester, (methyl) vinylformic acid-10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid-12-hydroxylauric ester or methacrylic acid (4-hydroxymethylcyclohexyl) methyl esters etc.; Containing sulfonic group monomer, as styrene sulfonic acid, allyl sulfonic acid, 2-(methyl) acrylamide-2-methylpro panesulfonic acid, (methyl) acryamidopropanesulfonic acid, (methyl) vinylformic acid sulphur propyl ester or (methyl) propane sulfonic acid etc.; Phosphorous acid-based monomers, as acryloyl phosphoric acid 2-hydroxy methacrylate etc.; Or styrene monomer.
(solidifying agent)
Described solidifying agent, as long as work as the solidifying agent of described nitrile group-containing thermoset acrylics base polymer, is not particularly limited, especially, during with epoxy group(ing) or Racemic glycidol radical reaction, preferably containing carboxyl, phenolic hydroxyl group, amino, acid anhydrides, wherein, preferred phenolic hydroxyl group.Can enumerate such as: phenol resol resins, phenol biphenyl resin (Off ェ ノ ー Le PVC Off ェ ニ Le Trees fat), phenol aralkyl resin (Off ェ ノ ー Le ア ラ Le キ Le Trees fat), cresol novolac resin, t-butylphenol novolac resin, the novolak phenolics such as nonylphenol novolac resin, the resol such as resol-type phenolic resin, the polycarboxylated styrenes etc. such as poly(4-hydroxystyrene), alizarin, low molecule the material more than difunctionalitys such as Whitfield's ointment, the benzo of phenolic hydroxyl group is there is by heat piperazine etc.These solidifying agent may be used singly or two or more in combination.
The weight-average molecular weight of described solidifying agent is not particularly limited, preferably in the scope of 100 ~ 3000, more preferably in the scope of 150 ~ 2000.When weight-average molecular weight is more than 100, the volatilization in solidifying can be suppressed, suppress the generation in space.On the other hand, when weight-average molecular weight is less than 3000, can prevent from becoming high viscosity, workability when die bonding film makes can be improved.
In addition, in die bonding film 3,3 ', suitably filler can be coordinated according to its purposes.The cooperation of filler can be given electroconductibility or improve thermal conductivity, adjustable elastic modulus etc.As described filler, mineral filler and organic filler can be enumerated, from the viewpoint of raising operability, improve the characteristics such as pyro-conductivity, adjustment melt viscosity, imparting thixotropy, preferred mineral filler.As described mineral filler, be not particularly limited, can enumerate such as: aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesiumcarbonate, Calucium Silicate powder, Magnesium Silicate q-agent, calcium oxide, magnesium oxide, aluminum oxide, aluminium nitride, aluminium borate whisker, boron nitride, crystalline silica, amorphous silica etc.These fillers may be used singly or two or more in combination.From the viewpoint of raising pyro-conductivity, preferential oxidation aluminium, aluminium nitride, boron nitride, crystalline silica, amorphous silica.In addition, good from the viewpoint of above-mentioned each balance of properties, preferred crystalline silica or amorphous silica.In addition, in order to give electroconductibility, improve the objects such as pyro-conductivity, conductive material (conductive filler material) also can be used as mineral filler.As conductive filler material, can enumerate and silver, aluminium, gold, copper, nickel, electroconductibility alloy etc. are formed as spherical, needle-like, flake and the metal oxide such as metal powder, aluminum oxide obtained, amorphous carbon black, graphite etc.
The median size of described filler is preferably 0.005 ~ 10 μm, more preferably 0.001 ~ 1 μm.This is because: by the median size of described filler is set as more than 0.005 μm, the wettability to adherend and tackiness can be improved.In addition, by being set as less than 10 μm, fully can realizing the effect of the filler added for giving above-mentioned each characteristic, and can thermotolerance be guaranteed.In addition, the median size of filler is such as the value obtained by luminosity formula size-grade distribution meter (HORIBA system, device name: LA-910).
The use level of described filler, overallly relative to the die bonding film composition resin solid content of die bonding film (form) is preferably 0 ~ 60 % by weight, and more preferably 0 ~ 50 % by weight.
In addition, in die bonding film 3,3 ', except described filler, suitably can also coordinate other additive as required.As other additive, can enumerate such as: fire retardant, silane coupling agent or ion trap agent etc.As described fire retardant, can enumerate such as: antimonous oxide, antimony peroxide, brominated epoxy resin etc.These fire retardants may be used singly or two or more in combination.As described silane coupling agent, can enumerate such as: β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl diethoxy silane etc.These silane coupling agents may be used singly or two or more in combination.As described ion trap agent, can enumerate such as: hydrotalcite, bismuth hydroxide etc.These ion trap agent may be used singly or two or more in combination.
The thickness (being total thickness when duplexer) of die bonding film 3,3 ' is not particularly limited, and such as, can select in the scope of 5 ~ 100 μm, preferably 5 ~ 50 μm.
The die bonding film 3,3 ' of described dicing/die bonding film 10,12, is preferably undertaken protecting (not shown) by partition.Partition has the function as the protecting materials of protect IC bonding film 3,3 ' before supply practicality.In addition, partition also can use to support base material during binder layer 2 transfer printing as by die bonding film 3,3 '.Partition is peeled off when the die bonding film 3,3 ' to dicing/die bonding film above pastes workpiece.As partition, polyethylene terephthalate (PET), polyethylene, polypropylene can be used, carry out plastics film, paper etc. after surface coated by strippers such as fluorine-containing type stripper, chain alkyl acrylate type strippers.
Described base material 1 has UV transmissive, and as the intensity parent of dicing/die bonding film 10,12.Can enumerate such as: polyolefine is as Low Density Polyethylene, linear polyethylene, medium-density polyethylene, high density polyethylene(HDPE), ultra-low density polyethylene, atactic copolymerized polypropene, block copolymerization polypropylene, homo-polypropylene, polybutene, polymethylpentene etc., vinyl-vinyl acetate copolymer, ionomer resin, ethene-(methyl) acrylic copolymer, ethene-(methyl) acrylate is (random, alternately) multipolymer, ethylene-butene copolymer, ethylene-hexene co-polymers, urethane, polyester is as polyethylene terephthalate, PEN etc., polycarbonate, polyimide, polyether-ether-ketone, polyimide, polyetherimide, polymeric amide, Wholly aromatic polyamide, polyphenylene sulfide, aromatic poly amide (paper), glass, woven fiber glass, fluorine resin, polyvinyl chloride, polyvinylidene dichloride, cellulosic resin, polyorganosiloxane resin, metal (paper tinsel), paper etc.
In addition, as the material of base material 1, the polymkeric substance such as the crosslinked of aforementioned resin can be enumerated.Described plastics film can not stretch and use, and uses after also can carrying out single shaft or biaxial stretch-formed process as required.Utilize the resin sheet being imparted heat-shrinkable by stretch processing etc., by making this base material 1 thermal contraction after dicing, the gluing area of binder layer 2 and die bonding film 3,3 ' can be reduced, thus easily can reclaim semi-conductor chip (semiconductor element).
In order to improve and the adhesivity of adjoining course, retentivity etc., usual surface treatment can be implemented in the surface of base material 1, such as, the chemistry such as chromic acid process, ozone exposure, fire exposure, high-voltage electric shock exposure, ionizing ray process or physical treatment, the coating process of silane coupling agent (such as adhesive substance described later) is utilized.Described base material 1 can the suitably of the same race or different types of material of choice for use, also can use as required several materials is blended after material.
The thickness of base material 1 is not particularly limited, and can suitably determine, is generally about 5 μm ~ about 200 μm.
The tackiness agent used in formation as binder layer 2 is not particularly limited, and can use the pressure sensitive adhesive that such as acrylic adhesives, rubber adhesive etc. are general.As described pressure sensitive adhesive, from the viewpoint of the clean detergency etc. utilizing the organic solvent such as ultrapure water or alcohols of electronic unit that the taboo such as semiconductor wafer or glass pollutes, the preferably acrylic adhesives of polymkeric substance based on acrylic polymers.
As described acrylic polymers, can enumerate such as: use (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, isopentyl ester, own ester, heptyl ester, monooctyl ester, 2-ethylhexyl, different monooctyl ester, the ninth of the ten Heavenly Stems ester, the last of the ten Heavenly stems ester, isodecyl ester, undecane ester, dodecane ester, tridecane ester, tetradecane ester, n-Hexadecane ester, octadecane ester, the carbonatoms 1 ~ 30 of the alkyl such as eicosane ester, the particularly straight or branched alkyl ester etc. of carbonatoms 4 ~ 18) and (methyl) acrylate ester is (such as, ring pentyl ester, cyclohexyl etc.) in one or more acrylic polymerss etc. as monomer component.In addition, (methyl) acrylate represents acrylate and/or methacrylic ester, and (methyl) of the present invention all represents identical implication.
In order to improve cohesive force, thermotolerance etc., described acrylic polymers as required can containing with can with unit corresponding to other monomer component of described (methyl) alkyl acrylate or the copolymerization of cycloalkanes ester.As such monomer component, can enumerate such as: carboxyl group-containing monomer, as vinylformic acid, methacrylic acid, (methyl) carboxyethyl acrylates, (methyl) vinylformic acid carboxyl pentyl ester, methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid etc.; Anhydride monomers, as maleic anhydride, itaconic anhydride etc.; Hydroxyl monomer, as (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-4-hydroxybutyl, the own ester of (methyl) vinylformic acid-6-hydroxyl, (methyl) vinylformic acid-8-hydroxyl monooctyl ester, (methyl) vinylformic acid-10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid-12-hydroxylauric ester, (methyl) vinylformic acid (4-hydroxymethylcyclohexyl) methyl esters etc.; Containing sulfonic group monomer, as styrene sulfonic acid, allyl sulfonic acid, 2-(methyl) acrylamide-2-methylpro panesulfonic acid, (methyl) acryamidopropanesulfonic acid, (methyl) vinylformic acid sulphur propyl ester, (methyl) acryloyl-oxy naphthene sulfonic acid etc.; Phosphorous acid-based monomers, as acryloyl phosphoric acid-2-hydroxy methacrylate etc.; Acrylamide, vinyl cyanide etc.These copolymerisable monomer compositions can use one or more.The usage quantity of these copolymerisable monomers is preferably less than 40 % by weight of whole monomer component.
In addition, described acrylic polymers in order to carry out crosslinked as required also can containing polyfunctional monomer etc. as comonomer composition.As such polyfunctional monomer, can enumerate such as: hexylene glycol two (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, epoxy (methyl) acrylate, polyester (methyl) acrylate, carbamate (methyl) acrylate etc.These polyfunctional monomers also can use one or more.The usage quantity of polyfunctional monomer is considered to be preferably less than 30 % by weight of whole monomer component from viewpoints such as adhesion characteristics.
Described acrylic polymers can by obtaining the polymerization of mixtures of single monomer or two or more monomer.Polymerization can be undertaken by any-modes such as solution polymerization, letex polymerization, mass polymerization, suspension polymerizations.From preventing from considering viewpoints such as the pollutions of clean adherend, the poor acrylic polymers of preferred low molecular weight substance.From this point to consider, the number-average molecular weight of acrylic polymers is preferably about more than 300,000, and more preferably from about 400,000 ~ about 3,000,000.
In addition, in order to the number-average molecular weight of the acrylic polymers etc. of polymkeric substance based on improving, in described tackiness agent, also suitably external crosslinker can be adopted.The concrete means of outside cross-linking method can be enumerated: add the so-called linking agents such as polyisocyanate compound, epoxy compounds, aziridine cpd, melamine class linking agent and the method making it react.When using external crosslinker, its usage quantity according to the balance of the base polymer that should be cross-linked and as tackiness agent use and suitably determine.Generally speaking, preferably coordinate below about 5 weight parts relative to described base polymer 100 weight part, more preferably coordinate 0.1 ~ 5 weight part.In addition, as required, in tackiness agent, except aforesaid ingredients, the in the past known additive such as various tackifier, antiaging agent can also be used.
Binder layer 2 can be formed by radiation curable tackiness agent.Radiation curable tackiness agent can increase degree of crosslinking by the irradiation of ultraviolet israds thus easily reduce its bounding force, by only to the part 2a illumination radiation line corresponding with workpiece adhesive portion of the binder layer 2 shown in Fig. 2, the difference with the bounding force of other parts 2b can be set.
In addition, by making the binder layer 2 of radiation curable solidify according to the die bonding film 3 ' shown in Fig. 2, the described part 2a that bounding force significantly declines can easily be formed.On the described part 2a that bounding force declines because die bonding film 3 ' is pasted onto solidification, the character easily peeled off when therefore the described part 2a of binder layer 2 and the interface of die bonding film 3 ' have pickup.On the other hand, the part of non-illumination radiation line has sufficient bounding force, forms described part 2b.
As previously mentioned, in the binder layer 2 of the dicing/die bonding film 10 shown in Fig. 1, the described part 2b formed by uncured radiation curable tackiness agent and die bonding film 3 bond, thus can guarantee confining force when cutting.Like this, radiation curable tackiness agent can with good gluing-peel off balanced support for shaped like chips workpiece (semi-conductor chip) being affixed to the die bonding film 3 on adherend.In the binder layer 2 of the dicing/die bonding film 11 shown in Fig. 2, paster ring (waferring) can be fixed by described part 2b.
Radiation curable tackiness agent can use without particular limitation to be had carbon-to-carbon double bond israds solidified nature functional group and shows fusible radiation curable tackiness agent.As radiation curable tackiness agent, can illustrate such as: in the pressure sensitive adhesive that described acrylic adhesives, rubber adhesive etc. are general, be combined with the monomer component of radiation curing or the addition type radiation curable tackiness agent of oligopolymer composition.
As the radiation curing monomer component for coordinating, can enumerate such as: oligourethane, carbamate (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylol methane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol monohydroxy five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, BDO two (methyl) acrylate etc.In addition, radiation curing oligopolymer composition can enumerate the various oligopolymer such as amino formate, polyethers, polyester, polycarbonate-based, polybutadiene, and its molecular weight is suitable in the scope of about 100 ~ about 30000.The use level of radiation curing monomer component or oligopolymer composition suitably can determine the amount of the bounding force that can reduce binder layer according to the kind of described binder layer.Generally speaking, relative to base polymer 100 weight part such as acrylic polymers forming tackiness agent, such as, be about 5 weight parts ~ about 500 weight parts, preferably about 40 weight parts ~ about 150 weight parts.
In addition, as radiation curable tackiness agent, except the addition type radiation curable tackiness agent illustrated above, can also enumerate and be used in polymer lateral chain or main chain or the inherent type radiation curable tackiness agent of polymkeric substance based on polymkeric substance that main chain terminal has a carbon-carbon double bond.Inherent type radiation curable tackiness agent is without the need to containing or not containing the oligopolymer composition etc. as low molecular weight compositions in a large number, therefore oligopolymer composition etc. can not be passed in time and move in tackiness agent, the binder layer of stable Rotating fields can be formed, therefore preferably.
The described base polymer with carbon-carbon double bond, can use without particular limitation and have carbon-carbon double bond and have fusible polymkeric substance.As such base polymer, preferably using acrylic polymers as the polymkeric substance of basic framework.As the basic framework of acrylic polymers, the acrylic polymers that foregoing illustrative is crossed can be enumerated.
In described acrylic polymers, the introducing method of carbon-carbon double bond is not particularly limited, and can adopt various method, method carbon-carbon double bond being introduced polymer lateral chain in molecular designing than being easier to.Can enumerate such as: will monomer and the acrylic polymers copolymerization of functional group be had in advance, then, make to have and can carry out the method for condensation or addition reaction with the compound of the functional group of this functional group reactions and carbon-carbon double bond under the situation of radiation curing keeping carbon-carbon double bond.
As the combination example of these functional groups, can enumerate such as: carboxyl and epoxy group(ing), carboxyl and '-aziridino, hydroxyl and isocyanate group etc.In the combination of these functional groups, consider the easiness that reaction is followed the tracks of, the combination of preferred hydroxyl and isocyanate group.In addition, as long as have the combination of the acrylic polymers of carbon-carbon double bond described in being generated by the combination of these functional groups, then functional group can in any one in acrylic polymers and described compound, for described preferably combination, the situation that preferred acrylic polymers has hydroxyl, described compound has isocyanate group.Now, as the isocyanate compound with carbon-carbon double bond, can enumerate such as: methacryloyl isocyanic ester, 2-methylacryoyloxyethyl isocyanic ester, a pseudoallyl-α, alpha-alpha-dimethyl dibenzoyl isocyanic ester etc.In addition, as acrylic polymers, the polymkeric substance of ether compound that copolymerization can be used to have the hydroxyl monomer of foregoing illustrative or 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl base ether such etc.
There is described in described inherent type radiation curable tackiness agent can be used alone the base polymer (particularly acrylic polymers) of carbon-carbon double bond, also can coordinate described radiation curing monomer component or oligopolymer composition in the scope not damaging characteristic.Radiation curing oligopolymer composition etc. relative to base polymer 100 weight part usually in the scope of 30 weight parts, the preferably scope of 0 ~ 10 weight part.
When by solidifications such as ultraviolets, in described radiation curable tackiness agent, Photoepolymerizationinitiater initiater can be contained.As Photoepolymerizationinitiater initiater, can enumerate such as: α-one alcohol compound, as 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone, Alpha-hydroxy-α, α '-dimethyl acetophenone, 2-methyl-2-hydroxypropiophenonepreparation, 1-hydroxycyclohexylphenylketone etc.; Acetophenone compounds, as methoxyacetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenones, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone etc.; Benzoin ether compounds, as ethoxybenzoin, benzoin iso-propylether, anisoin methyl ether etc.; Ketal compounds, as dibenzoyl dimethyl ketal etc.; Aromatic sulfonyl compounds, as 2-naphthalic sulfonic chloride etc.; Photolytic activity oxime compounds, as 1-phenyl-1,2-propanedione-2-(O-ethoxy carbonyl) oxime etc.; Benzophenone compound, as benzophenone, benzoylbenzoic acid, 3,3 '-dimethyl-4-methoxy benzophenone etc.; Thioxanthone compounds, as thioxanthone, CTX, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-bis-clopenthixal ketones, 2,4-diethyl thioxanthones, 2,4-diisopropylthioxanthone etc.; Camphorquinone; Halogenated ketone; Acylphosphine oxide; Acyl phosphonate etc.The use level of Photoepolymerizationinitiater initiater relative to base polymer 100 weight part such as acrylic polymers forming tackiness agent, such as, is about 0.05 weight part ~ about 20 weight parts.
In addition, as radiation curable tackiness agent, can enumerate such as: disclosed in Japanese Laid-Open Patent Publication 60-196956 publication, containing have the polyaddition compound of more than 2 unsaturated link(age)s, the photopolymerizable compound such as organoalkoxysilane with epoxy group(ing) and carbonyl compound, organosulfur compound, superoxide, amine, the rubber adhesive of the Photoepolymerizationinitiater initiaters such as salt compounds or acrylic adhesives etc.
In the binder layer 2 of described radiation curable, as required also can containing the painted compound by illumination radiation line.By containing by illumination radiation line painted compound in binder layer 2, can only by the colored parts of illumination radiation line.That is, can by painted for the part 2a corresponding with workpiece adhesive portion 3a shown in Fig. 1.Thus, can directly judge the whether illuminated radiation of binder layer 2 by naked eyes, can easily identify workpiece adhesive portion 3a, the stickup of workpiece is also easy.In addition, when utilizing optical sensor etc. to detect semiconductor element, its accuracy of detection is high, thus does not produce mishandle when the pickup of semiconductor element.
The painted compound by illumination radiation line, but for colourless before illumination radiation line or light by illumination radiation line and coloured compound.As the preferred concrete example of described compound, leuco dye (ロ イ コ dyestuff) can be enumerated.As leuco dye, usual triphenylmethane, Material of Fluoran, phenothiazines, auramine class, spiro-pyrans class leuco dye preferably can be used.Can enumerate particularly: 3-[N-(p-methylphenyl is amino)]-7-anilino fluorane, 3-[N-(p-methylphenyl)-N-methylamino]-7-anilino fluorane, 3-[N-(p-methylphenyl)-N-ethylamino]-7-anilino fluorane, 3-diethylin-6-methyl-7-anilino fluorane, crystal violet lactone, 4,4 '; 4 "-three (dimethylamino) triphenylcarbinol, 4,4 ', 4 "-three (dimethylamino) triphenyl methane etc.
As the preferred developer used together with these leuco dyes, the electron acceptor(EA)s such as the prepolymer of the resol all the time used, aromatic derivant carboxylate, atlapulgite can be enumerated, in addition, when making tonal variation, various chromogenic reagent can be combinationally used.
Like this by illumination radiation line and painted compound, first can be dissolved in after in organic solvent etc. and cover in radiation curable tackiness agent again, in addition, also can comprise in the adhesive in fine powder form.The usage ratio of this compound wishes to be less than 10 % by weight in binder layer 2, preferably 0.01 ~ 10 % by weight, more preferably 0.5 ~ 5 % by weight.When the ratio of this compound is more than 10 % by weight, be irradiated to the radiation of binder layer 2 by this compound taken in excess, therefore the solidification of the described part 2a of binder layer 2 is insufficient, and bounding force declines insufficient sometimes.On the other hand, in order to fully painted, preferably the ratio of this compound is set as more than 0.01 % by weight.
When forming binder layer 2 by radiation curable tackiness agent, preferably the bounding force that irradiation with radiation makes the bounding force < other parts 2b of part 2a described in binder layer 2 is carried out to a part for binder layer 2.
As the method forming described part 2a in described binder layer 2, can enumerate: form radiation-curable adhesive layer 2 on base material 1 after, to the described part 2a illumination radiation line method that makes it solidify partly.The irradiation with radiation of local can be undertaken by the photomask being formed with the pattern corresponding with the part 3b beyond workpiece adhesive portion 3a etc.In addition, the method etc. that point-like irradiation ultraviolet radiation is cured can be enumerated.The formation of radiation-curable adhesive layer 2 can be undertaken by the radiation-curable adhesive layer be arranged on partition being transferred on support base material 1.The radiation curing of local also can carry out the radiation-curable adhesive layer 2 be arranged on partition.
In addition, when forming binder layer 2 by radiation curable tackiness agent, the whole of the part beyond to the part corresponding with workpiece adhesive portion 3a of at least one side of support base material 1 or local can be used to carry out the base material of shading, and carry out irradiation with radiation after forming radiation-curable adhesive layer 2 on the substrate, make corresponding with workpiece adhesive portion 3a partially cured, thus form the described part 2a that bounding force declines.As light screening material, the material that can become photomask can be made by printing or evaporation etc. in support film.By described manufacture method, dicing/die bonding film 10 of the present invention effectively can be manufactured.
In addition, when carrying out irradiation with radiation because of oxygen produce solidification obstacle when, preferably utilize any means from the surperficial isolating oxygen (air) of radiation-curable adhesive layer 2.Can enumerate such as: with partition by the method for the surface coverage of binder layer 2 or the method etc. of irradiation of carrying out ultraviolet israds in nitrogen atmosphere.
The thickness of binder layer 2 is not particularly limited, and from realizing preventing the viewpoint such as the defect in chip cutting face and the fixing maintenance of adhesive layer from considering simultaneously, is preferably about 1 μm to about 50 μm.Preferably 2 μm ~ 30 μm, more preferably 5 μm ~ 25 μm.
The dicing/die bonding film 10,12 of present embodiment, such as, make as follows.
First, base material 1 can by existing known film-forming method masking.As this film-forming method, can illustrate such as: the casting in calendering masking method, organic solvent, blowing extrusion molding, T-shaped extrusion, coetrusion, dry lamination method etc. in enclosed system.
Then, on base material 1, coating adhesive composition solution forms film, then in predefined conditions this dried coating film (as required heat cross-linking) is formed binder layer 2.As coating process, be not particularly limited, can enumerate such as: the coating of roller coat, silk screen, intaglio plate coating etc.In addition, as drying conditions, can such as: carry out in drying temperature 80 ~ 150 DEG C, the scope of 0.5 ~ 5 minute time of drying.In addition, also on partition, under described drying conditions, dried coating film can be formed binder layer 2 after forming film by coating adhesive composition.Then, binder layer 2 is pasted on base material 1 together with partition.Thus, cutting film 11 is made.
Die bonding film 3,3 ' such as makes as follows.
First, the adhesive compound solution of the formation material as dicing/die bonding film 3,3 ' is made.In this adhesive compound solution, as previously mentioned, described adhesive compound, filler, other various additives etc. are combined with.
Then, in the mode obtaining pre-determined thickness, adhesive compound solution coat is formed film to base material partition, then in predefined conditions by this dried coating film, form adhesive layer.Be not particularly limited as coating process, can enumerate such as: the coating of roller coat, silk screen, intaglio plate coating etc.In addition, as drying conditions, such as, carry out in drying temperature 70 ~ 160 DEG C, the scope of 1 ~ 5 minute time of drying.In addition, also can on partition coating adhesive composition solution and after forming film, under aforementioned drying condition, dried coating film is formed adhesive layer.Then, adhesive layer is pasted on base material partition together with partition.
Then, respectively partition is peeled off from cutting film 11 and adhesive layer, as the mode of sticking veneer, both are pasted using adhesive layer and binder layer.Paste and such as can be undertaken by crimping.Now, laminating temperature is not particularly limited, such as preferably 30 ~ 50 DEG C, more preferably 35 ~ 45 DEG C.In addition, line pressure is also not particularly limited, such as preferably 0.1 ~ 20kgf/cm, more preferably 1 ~ 10kgf/cm.Then, the base material partition on adhesive layer is peeled off, obtains the dicing/die bonding film of present embodiment.
(manufacture method of semiconductor device)
Dicing/die bonding film 10,12 of the present invention, suitably peels off the partition be arranged on arbitrarily on die bonding film 3,3 ' and following use.Below, be described to use the situation of dicing/die bonding film 10 with reference to figure 3.Fig. 3 is the schematic sectional view of the example represented by the adhesive layer mounting semiconductor chip in the dicing/die bonding film shown in Fig. 1.
First, semiconductor wafer 4 is crimped onto on the semiconductor wafer adhesive portion 3a of the die bonding film 3 in dicing/die bonding film 10, its gluing maintenance is fixed (adhering processes).This operation utilizes the extruding means extruding such as crimping roller to carry out.Sticking temperature during installation is not particularly limited, and preference is as in the scope of 20 ~ 80 DEG C.
Then, the cutting of semiconductor wafer 4 is carried out.Thus, semiconductor wafer 4 is cut into predetermined size and panelization, makes semi-conductor chip 5.Cutting is such as conventionally carried out from the circuit face side of semiconductor wafer 4.In addition, in this operation, such as, cutting mode etc. that be cut into dicing/die bonding film 10, that be called full cutting can be adopted.The cutting unit used in this operation is not particularly limited, and can adopt existing known cutting unit.In addition, semiconductor wafer is gluing fixing by dicing/die bonding film 10, chip defect or chip therefore can be suppressed to disperse, and can suppress the breakage of semiconductor wafer 4.
In order to peel off by the gluing fixing semi-conductor chip of dicing/die bonding film 10, carry out the pickup of semi-conductor chip 5.Pick-up method is not particularly limited, and can adopt existing known various method.Can enumerate such as: with pin, each semi-conductor chip 5 is pushed away from dicing/die bonding film 10 side, and utilize pickup device to pick up the method etc. of the semi-conductor chip 5 above pushed away.
At this, when binder layer 2 is ultraviolet hardening, pick up after to this binder layer 2 irradiation ultraviolet radiation.Thus, the bounding force of binder layer 2 pairs of die bonding films 3 declines, and semi-conductor chip 5 is easily peeled off.As a result, can pick up when not damaging semi-conductor chip 5.The conditions such as exposure intensity during uviolizing, irradiation time are not particularly limited, and can suitably set as required.In addition, as the light source used during uviolizing, aforesaid light source can be used.
The semi-conductor chip 5 of pickup is fixed to (chip join) on adherend 6 by die bonding film 3 is gluing.
The condition of chip join is not particularly limited, and can suitably set.Such as, can be set as in chip join temperature 80 ~ 160 DEG C, chip join pressure 5N ~ 15N, the scope of 1 ~ 10 second chip join time.
As adherend 6, lead frame, TAB film, substrate or the independent semi-conductor chip etc. made can be enumerated.Adherend 6 can be such as hold yielding deformation type adherend, also can be the non-deformed type adherend (semiconductor wafer etc.) being difficult to be out of shape.
As described substrate, existing known substrate can be used.In addition, described lead frame can use the die-attach area such as Cu lead frame, 42 alloy lead wire frames or comprise the RF magnetron sputtering of glass epoxide, BT (bismaleimide-triazine), polyimide etc.But, the present invention is not limited thereto, also comprise and semiconductor element is installed and is electrically connected and operable circuit card with semiconductor element.
When die bonding film 3 is thermohardening type, by being heating and curing, semi-conductor chip 5 being adhesively fixed and fixing on adherend 6, high-temperature capability is improved.Can be 80 ~ 180 DEG C in Heating temperature, carry out at preferably 100 ~ 175 DEG C, more preferably 100 ~ 150 DEG C.In addition, can be 0.1 ~ 24 hour in heat-up time, preferably 0.1 ~ 3 hour, more preferably 0.1 ~ 1 are little carries out at present.
The clipping viscous force of the die bonding film 3 pairs of adherends 6 after thermofixation is preferably more than 0.02MPa, more preferably 0.03 ~ 10MPa.The clipping viscous force of die bonding film 3 be at least more than 0.02MPa time, when carrying out wire bond operation, shearing strain can not be produced because of the ultrasonic vibration in this operation or heating on the gluing surface of die bonding film 3 and semi-conductor chip 5 or adherend 6.That is, semiconductor element can not be movable because of ultrasonic vibration during wire bond, thus, can prevent the success ratio of wire bond from declining.
In addition, the manufacture method of semiconductor device of the present invention, when carrying out wire bond without when the heat curing processes utilizing heat treated to carry out of die bonding film 3, then can seal semi-conductor chip 5 with sealing resin, and by sealing resin after fixing.Now, more than 0.02MPa is preferably to the clipping viscous force of adherend 6, more preferably 0.03 ~ 10MPa during die bonding film 3 temporarily set.Clipping viscous force during die bonding film 3 temporarily set be at least more than 0.02MPa time, even if when carrying out wire bond operation without when heating process, also seldom shearing strain can be produced because of the ultrasonic vibration in this operation or heating on the gluing surface of die bonding film 3 and semi-conductor chip 5 or adherend 6.That is, semiconductor element can not be movable because of ultrasonic vibration during wire bond, thus, can prevent the success ratio of wire bond from declining.
Described wire bond is the operation (with reference to figure 3) utilizing bonding wire 7 to be electrically connected with the electrode pad (not shown) on semi-conductor chip 5 front end of the portion of terminal (inner lead) of adherend 6.As described bonding wire 7, can use such as: gold thread, aluminum steel or copper cash etc.Temperature when carrying out wire bond is carried out in the scope of 80 ~ 250 DEG C, preferably 80 ~ 220 DEG C.In addition, several seconds ~ several minutes is carried out its heat-up time.Wiring is in described temperature range under heating condition, and the crimping by combinationally using ultrasonic vibration and applying pressure and produce can be carried out.This operation can be carried out when not carrying out the thermofixation of die bonding film 3.
Described sealing process is the operation (with reference to figure 3) utilizing sealing resin 8 to be sealed by semi-conductor chip 5.This operation is mounted in semi-conductor chip 5 on adherend 6 or bonding wire 7 carries out to protect.This operation is by carrying out with the resin forming of mould by sealing.As sealing resin 8, such as, redix can be used.Heating temperature during resin seal carries out 60 ~ 90 seconds usually at 175 DEG C, but, the present invention is not limited thereto, such as, also can solidify several minutes at 165 ~ 185 DEG C.Thus, while making sealing resin solidify by die bonding film 3 by semi-conductor chip 5 and adherend 6 set.That is, in the present invention, even if when not carrying out after fixing operation described later, die bonding film 3 in this operation, also can be utilized to carry out set, thus the manufacturing time reducing worker ordinal number and shortening semiconductor device can be contributed to.
In described after fixing operation, make in aforementioned seal operation, solidify not enough sealing resin 8 and solidify completely.Even if when sealing process chips bonding film 3 not completely thermofixation, in this operation, also can realize the complete thermofixation of die bonding film 3 together with sealing resin 8.Heating temperature in this operation is different because of the kind of sealing resin, and such as, in the scope of 165 ~ 185 DEG C, heat-up time is about 0.5 hour ~ about 8 hours.
Then, at printed wiring board upper surface, described semiconductor packages is installed.The method of surface mounting can be enumerated such as: supply solder in advance on printed wiring board after, utilizes warm air etc. to carry out heating and melting and carries out the reflow soldering (reflow soldering operation) of welding.As heating means, hot air reflux, infrared rays backflow etc. can be enumerated.In addition, can be any one mode in overall heating, local heating.Heating temperature is preferably 230 ~ 280 DEG C, and heat-up time is preferably in the scope of 1 ~ 360 second.
In addition, dicing/die bonding film of the present invention, as shown in Figure 4, also can suitably for carrying out three-dimensional situation of installing by stacked for multiple semi-conductor chip.Fig. 4 is the schematic sectional view of the example represented by the three-dimensional mounting semiconductor chip of the adhesive layer in the dicing/die bonding film shown in Fig. 1.When three-dimensional shown in Fig. 4 is installed, first, by being cut into at least one die bonding film 3 chip join of semi-conductor chip same size on adherend 6, then, by die bonding film 3, semi-conductor chip 5 is carried out chip join in the mode that its wire bond face is upside.Then, die bonding film 13 is carried out chip join by the electrode pad portion avoiding semi-conductor chip 5.And then, by another semi-conductor chip 15 with its wire bond face mode chip join that is upside on die bonding film 13.
Then, carry out the thermofixation of die bonding film 3,3 ', then carry out wire bond operation.Thus, with bonding wire 7, electrode pad respective in semi-conductor chip 5 and second half conductor chip 15 is electrically connected with adherend 6.
Then, utilize sealing resin 8 to carry out sealing process semi-conductor chip 5 grade sealed, and sealing resin is solidified.In addition, after fixing operation can be carried out after sealing process.
When carrying out the three-dimensional installation of semi-conductor chip, bonding wire 7 increasing number be connected with adherend 6 by semi-conductor chip 5,15, therefore has the tendency of the time increase spent in wire bond operation, thus at high temperature exposes for a long time.But, by die bonding film 3,13, even if at high temperature expose for a long time, the carrying out that thermofixation is reacted also can be suppressed.
In addition, can carry out as shown in Figure 5 being installed by the three-dimensional of the stacked pad of die bonding film between semi-conductor chip.Fig. 5 represents to use the dicing/die bonding film shown in Fig. 1, across the schematic sectional view of the example that pad utilizes adhesive layer two semi-conductor chip three-dimensionals to be installed.
When three-dimensional shown in Fig. 5 is installed, first, adherend 6 stacks gradually die bonding film 3, semi-conductor chip 5 and die bonding film 21.In addition, on die bonding film 21, stack gradually partition 9, die bonding film 21, die bonding film 3 and semi-conductor chip 5 and carry out chip join.
Then, carry out the thermofixation of die bonding film 3,21, then, carry out wire bond operation as shown in Figure 5.Thus, bonding wire 7 is utilized to be electrically connected with adherend 6 by the electrode pad in semi-conductor chip 5.
Then, carry out the sealing process utilizing sealing resin 8 to be sealed by semi-conductor chip 5, and sealing resin is solidified.Thus, semiconductor packages is obtained.Sealing process is preferably only by the once sealing method of semi-conductor chip 5 side single facer.Sealing is carried out to protect the semi-conductor chip 5 be pasted onto on adhesive sheet, and its method is shaped to representative in a mold to use sealing resin 8.Now, be generally use the mould be made up of upper die and lower die with multiple chamber, carry out sealing process simultaneously.Heating temperature during resin seal is such as preferred in the scope of 170 ~ 180 DEG C.After sealing process, after fixing operation can be carried out.
In addition, as described pad 9, be not particularly limited, such as, can use existing known silicon, Kapton etc.In addition, core can be used as described pad.Be not particularly limited as core, existing known core can be used.Specifically, resin substrates, minute surface silicon wafer, silicon substrate or the glass substrate etc. that can use film (such as, Kapton, polyester film, pet film, PEN film, polycarbonate film etc.), are strengthened by glass fibre or plastics non-woven fibre.
Then, described semiconductor package surface is installed by printed wiring board.The method of surface mounting can be enumerated such as: supply solder in advance on printed wiring board after, utilizes warm air etc. to carry out heating and melting and carries out the reflow soldering of welding.As heating means, hot air reflux, infrared rays backflow etc. can be enumerated.In addition, can be any one mode in overall heating, local heating.Heating temperature is preferably 230 ~ 280 DEG C, and heat-up time is preferably in the scope of 1 ~ 360 second.
Embodiment
Below, the preferred embodiments of the present invention are described in detail illustratively.But the material recorded in this embodiment, use level etc., if the record of being not particularly limited to property, then not only limit the invention to this.In addition, " part " refers to weight part.
(mensuration of oxirane value)
The oxirane value of the nitrile group-containing thermoset acrylics analog copolymer used in the present embodiment, comparative example calculates according to JISK7236.Specifically, 4g nitrile group-containing thermoset acrylics analog copolymer is weighed in the Erlenmeyer flask of 100ml, adds 10ml chloroform wherein and dissolved.Add 30ml acetic acid, 5ml tetraethylammonium bromide and 5 Viola crystallina indicator again, while by magnetic stirrer, carry out titration with the perchloric acid acetic acid normal solution of 0.1mol/L.Carry out blank test by same method, and utilize following formula ring oxygen value.
Oxirane value=[(V-B) × 0.1 × F]/W
W: the grams of the sample of weighing
B: the milliliter number of the 0.1mol/L perchloric acid acetic acid normal solution required for blank test
V: the milliliter number of the 0.1mol/L perchloric acid acetic acid normal solution required for the titration of sample
The factor of F:0.1mol/L perchloric acid acetic acid normal solution
(mensuration of second-order transition temperature (Tg))
The second-order transition temperature of the nitrile group-containing thermoset acrylics analog copolymer used in the present embodiment, comparative example, (RheometricScientific company manufactures to use determination of viscoelasticity device, RSA-III), measured by the Tan (E " (loss Young's modulus)/E ' (store elastic modulus)) under heat-up rate 10 DEG C/min, frequency 1MHz.
(mensuration of the weight-average molecular weight of nitrile group-containing thermoset acrylics analog copolymer)
The weight-average molecular weight of the nitrile group-containing thermoset acrylics analog copolymer used in the present embodiment, comparative example, passes through gel permeation chromatography.In gel permeation chromatography, these 4 posts (being TOSOH Co., Ltd's system) of TSKG2000HHR, G3000HHR, G4000HHR and GMH-HHR are connected in series use, use tetrahydrofuran (THF) as elutriant, flow velocity 1ml/ minute, temperature 40 DEG C, sample solution concentration 0.1 % by weight tetrahydrofuran solution, sample injection amount 500 μ l condition under carry out, detector use differential refractometer.
(embodiment 1)
100 parts of nitrile group-containing thermoset acrylics analog copolymers (a-1), 5.2 parts of resol as solidifying agent (b-1) are dissolved in methylethylketone, the adhesive compound solution of preparation concentration 23.6 % by weight.As the nitrile group-containing thermoset acrylics analog copolymer (a-1) in embodiment 1, use with (Negami Chemical Ind Co., Ltd.'s manufacture of the acrylic polymer of acrylonitrile-ethacrylate-butyl acrylate for main component and containing 4.1 % by mole of glycidyl acrylates, ND series, suspension polymer, oxirane value 0.41, glass transition point (Tg) 12 DEG C, weight-average molecular weight 500,000).In addition, the content that vinyl cyanide is shared in nitrile group-containing thermoset acrylics analog copolymer (a-1) is 28 % by weight relative to the gross weight of multipolymer.In addition, as the resol (b-1) of the solidifying agent in embodiment 1, use bright " MEH7851 " with changing into Co., Ltd.'s manufacture.
On the demoulding process film (release liner) that this adhesive compound solution coat is formed to the pet film of the thickness after polysiloxane demoulding process 50 μm, then 130 DEG C of dryings 2 minutes.Thus, the die bonding film A of thickness 25 μm is made.
(embodiment 2)
100 parts of nitrile group-containing thermoset acrylics analog copolymers (a-2), 10.3 parts of resol as solidifying agent (b-2) are dissolved in methylethylketone, the adhesive compound solution of preparation concentration 23.6 % by weight.As the nitrile group-containing thermoset acrylics analog copolymer (a-2) in embodiment 2, use with (Negami Chemical Ind Co., Ltd.'s manufacture of the acrylic polymer of acrylonitrile-ethacrylate-butyl acrylate for main component and containing 4.1 % by mole of glycidyl acrylates, ND series, suspension polymer, oxirane value 0.41, glass transition point (Tg) 9 DEG C, weight-average molecular weight 1,050,000).In addition, the content that vinyl cyanide is shared in nitrile group-containing thermoset acrylics analog copolymer (a-2) is 24 % by weight relative to the gross weight of multipolymer.In addition, as the resol (b-2) of the solidifying agent in embodiment 2, use bright " MEH7851 " with changing into Co., Ltd.'s manufacture.
On the demoulding process film (release liner) that this adhesive compound solution coat is formed to the pet film of the thickness after polysiloxane demoulding process 50 μm, then 130 DEG C of dryings 2 minutes.Thus, the die bonding film B of thickness 25 μm is made.
(embodiment 3)
100 parts of nitrile group-containing thermoset acrylics analog copolymers (a-3), 48.5 parts of resol as solidifying agent (b-3) are dissolved in methylethylketone, the adhesive compound solution of preparation concentration 23.6 % by weight.As the nitrile group-containing thermoset acrylics analog copolymer (a-3) in embodiment 3, use with (Negami Chemical Ind Co., Ltd.'s manufacture of the acrylic polymer of acrylonitrile-ethacrylate-butyl acrylate for main component and containing 4.1 % by mole of glycidyl acrylates, ND series, suspension polymer, oxirane value 0.41, glass transition point (Tg) 0 DEG C, weight-average molecular weight 1,100,000).In addition, the content that vinyl cyanide is shared in nitrile group-containing thermoset acrylics analog copolymer (a-3) is 20 % by weight relative to the gross weight of multipolymer.In addition, as the resol (b-3) of the solidifying agent in embodiment 3, use bright " MEH7851 " with changing into Co., Ltd.'s manufacture.
On the demoulding process film (release liner) that this adhesive compound solution coat is formed to the pet film of the thickness after polysiloxane demoulding process 50 μm, then 130 DEG C of dryings 2 minutes.Thus, the die bonding film C of thickness 25 μm is made.
(embodiment 4)
Using 100 parts of nitrile group-containing thermoset acrylics analog copolymers (a-4), 10.3 parts as 1 of solidifying agent, 2,4-trihydroxybenzene (b-4) is dissolved in methylethylketone, disperse spherical silicon dioxide (ア De マ テ ッ Network ス Co., Ltd. system of 40 parts of median size 500nm further wherein, SO-25R), the adhesive compound solution of concentration 23.6 % by weight is prepared.As the nitrile group-containing thermoset acrylics analog copolymer (a-4) in embodiment 4, use with (Negami Chemical Ind Co., Ltd.'s manufacture of the acrylic polymer of acrylonitrile-ethacrylate-butyl acrylate for main component and containing 2.4 % by mole of glycidyl acrylates, ND series, suspension polymer, oxirane value 0.23, glass transition point (Tg) 0 DEG C, weight-average molecular weight 1,050,000).In addition, the content that vinyl cyanide is shared in nitrile group-containing thermoset acrylics analog copolymer (a-4) is 20 % by weight relative to the gross weight of multipolymer.In addition, as the THB (b-4) of the solidifying agent in embodiment 4, Tokyo is used to change into the product of Co., Ltd.'s manufacture.
On the demoulding process film (release liner) that this adhesive compound solution coat is formed to the pet film of the thickness after polysiloxane demoulding process 50 μm, then 130 DEG C of dryings 2 minutes.Thus, the die bonding film D of thickness 25 μm is made.
(comparative example 1)
100 parts of thermoset acrylics analog copolymers (a-5), 5.2 parts of resol as solidifying agent (b-3) are dissolved in methylethylketone, the adhesive compound solution of preparation concentration 23.6 % by weight.As the thermoset acrylics analog copolymer (a-5) in comparative example 1, use with (Negami Chemical Ind Co., Ltd.'s manufacture of the acrylic polymer of ethyl acrylate-acrylic acid butyl ester for main component and containing 4.1 % by mole of glycidyl acrylates, ND series, suspension polymer, oxirane value 0.41, glass transition point (Tg) 12 DEG C, weight-average molecular weight 900,000).In addition, as the resol (b-5) of the solidifying agent in comparative example 1, use bright " MEH7851 " with changing into Co., Ltd.'s manufacture.
On the demoulding process film (release liner) that this adhesive compound solution coat is formed to the pet film of the thickness after polysiloxane demoulding process 50 μm, then 130 DEG C of dryings 2 minutes.Thus, the die bonding film E of thickness 25 μm is made.
(comparative example 2)
Using 100 parts of nitrile group-containing thermoset acrylics analog copolymers (a-6), 10.3 parts of resol as solidifying agent (b-3) and 5 parts of curing catalysts, (four countries change into Co., Ltd. and manufacture, C11-Z) be dissolved in methylethylketone, the adhesive compound solution of preparation concentration 23.6 % by weight.As the nitrile group-containing thermoset acrylics analog copolymer (a-6) in comparative example 2, use with (Negami Chemical Ind Co., Ltd.'s manufacture of the acrylic polymer of acrylonitrile-ethacrylate-butyl acrylate for main component and containing 4.1 % by mole of glycidyl acrylates, ND series, suspension polymer, oxirane value 0.41, glass transition point (Tg) 9 DEG C, weight-average molecular weight 1,050,000).In addition, vinyl cyanide, containing content shared in nitrile thermoset acrylics analog copolymer (a-6), is 24 % by weight relative to multipolymer gross weight.In addition, as the resol (b-6) of the solidifying agent in comparative example 2, use bright " MEH7851 " with changing into Co., Ltd.'s manufacture.
On the demoulding process film (release liner) that this adhesive compound solution coat is formed to the pet film of the thickness after polysiloxane demoulding process 50 μm, then 130 DEG C of dryings 2 minutes.Thus, the die bonding film F of thickness 25 μm is made.
(thermal discharge mensuration)
During thermal discharge measures, use differential scanning calorimeter (SIINanoTechnology company manufactures, DSC6220).First, sample (die bonding film A ~ F) 10mg is put in band pleat aluminum pot (Al Network リ Application プ パ Application), in a nitrogen atmosphere, be warmed up to 300 DEG C with the heat-up rate of 10 DEG C/min from 25 DEG C (room temperatures).Draw base line in the DSC curve (exothermic peak) obtained in temperature-rise period, the areal calculation heat of the part surrounded by baseline and DSC curve.Fig. 6 represents the figure being measured the typical differential calorimetric curve obtained by means of differential scanning calorimetry.The area in the region that described heat is surrounded by the baseline B shown in Fig. 6 and differential calorimetric curve L calculates.
Then, thermal discharge is calculated by following formula.
(thermal discharge (mJ/mg))=(heat (mJ))/(measuring the weight (mg) of sample)
In addition, these operations and calculating are automatically carried out.Result is as shown in table 1.
The mensuration > of the stretching store elastic modulus at 25 DEG C before < thermofixation
Die bonding film A ~ F cutting knife is cut into the strip of length 22.5mm (measured length) × width 10mm, use solid determination of viscoelasticity device (RSA-III, RheometricScientific Co., Ltd. manufactures), measure the stretching store elastic modulus of-50 ~ 300 DEG C.Condition determination is, frequency 1Hz, heat-up rate 10 DEG C/min.The value of the stretching store elastic modulus of now 50 DEG C is as shown in table 1.
The stretching store elastic modulus > of < at after 5 hours 260 DEG C of 175 DEG C of thermofixations
By die bonding film A ~ F 175 DEG C of thermofixations 5 hours.Then, die bonding film A ~ F cutting knife after thermofixation is cut into the strip of length 22.5mm (measured length) × width 10mm, use solid determination of viscoelasticity device (RSA-III, RheometricScientific Co., Ltd. manufactures), measure the stretching store elastic modulus of-50 ~ 300 DEG C.Condition determination is, frequency 1Hz, heat-up rate 10 DEG C/min.The value of the stretching store elastic modulus of now 260 DEG C is as shown in table 1.
< with 175 DEG C of thermofixations after 5 hours for benchmark, the mensuration > of the temperature of weightless 5 % by weight
For at the die bonding film A ~ F of 175 DEG C of thermofixations after 5 hours, measured the temperature of weightless 5 % by weight by TGA.Result is as shown in table 1.
< is at the mensuration > of the water-intake rate of 175 DEG C of thermofixations after 5 hours
For die bonding film A ~ F, by 85 DEG C, the weight reduction rates placed before and after 168 hours is determined at the water-intake rate of 175 DEG C of thermofixations after 5 hours in the constant temperature and humidity cabinet of 85%RH.Result is as shown in table 1.
Bubble (space) deorienting after < sealing process (when 120 DEG C of thermal treatments 10 hours) >
Die bonding film A ~ the F obtained in each embodiment and comparative example is pasted under the condition of 40 DEG C on the square semiconductor element of 5mm, be then installed on BGA (ball grid array) substrate under temperature 120 DEG C, pressure 0.1MPa, the condition of 1 second time.Again with drying machine by it 150 DEG C of thermal treatments 1 hour, then implement the thermal treatment of 10 hours at 120 DEG C.Then, (TOWAPress company manufactures to use forming machine, マ ニ ュ ア Le プ レ ス Y-1), under the condition of forming temperature 175 DEG C, clamping pressure 184kN, transmission pressure 5kN, 120 seconds time, sealing resin GE-100 (Nitto Denko Corp's manufacture), carry out sealing process.Use ultrasound imaging device (FineTech company of Hitachi manufactures, FS200II) observes the interface of the die bonding film after sealing process and BGA substrate.Area in the image using binaryzation software (WinRoofver.5.6) calculating to observe shared by space.The average evaluation that area shared by space is less than 30% relative to the surface-area of die bonding film is "○", and the average evaluation of more than 30% is "×".Result is as shown in table 1.
Bubble (space) deorienting after < sealing process (when 175 DEG C of thermal treatments 1 hour) >
Die bonding film A ~ the F obtained in each embodiment and comparative example is pasted under the condition of 40 DEG C on the square semiconductor element of 5mm, be then installed on BGA (ball grid array) substrate under temperature 120 DEG C, pressure 0.1MPa, the condition of 1 second time.Again with drying machine by it 150 DEG C of thermal treatments 1 hour, then implement the thermal treatment of 1 hour at 175 DEG C.Then, (TOWAPress company manufactures to use forming machine, マ ニ ュ ア Le プ レ ス Y-1), under the condition of forming temperature 175 DEG C, clamping pressure 184kN, transmission pressure 5kN, 120 seconds time, sealing resin GE-100 (Nitto Denko Corp's manufacture), carry out sealing process.Use ultrasound imaging device (FineTech company of Hitachi manufactures, FS200II) observes the interface of the die bonding film after sealing process and BGA substrate.Area in the image using binaryzation software (WinRoofver.5.6) calculating to observe shared by space.The average evaluation that area shared by space is less than 30% relative to the surface-area of die bonding film is "○", and the average evaluation of more than 30% is "×".Result is as shown in table 1.
(moisture-proof reflow soldering test (when carrying out after thermal treatment in 10 hours for 120 DEG C))
Die bonding film A ~ the F obtained in each embodiment and comparative example is pasted at 40 DEG C on the square semi-conductor chip of 5mm, be then installed on BGA substrate under temperature 120 DEG C, pressure 0.1MPa, the condition of 1 second time.Again with drying machine by it 150 DEG C of thermal treatments 1 hour, then implement the thermal treatment of 10 hours at 120 DEG C.Then, (TOWAPress company manufactures to use forming machine, マ ニ ュ ア Le プ レ ス Y-1), under the condition of forming temperature 175 DEG C, clamping pressure 184kN, transmission pressure 5kN, 120 seconds time, sealing resin GE-100 (Nitto Denko Corp's manufacture), carry out sealing process.Then, under temperature 85 DEG C, humidity 60%RH, the condition of 168 hours time, carry out moisture absorption operation, then by sample by carrying out the IR reflow ovens of temperature setting in the mode temperature of more than 260 DEG C kept 30 seconds.For 9 semiconductor elements, whether the boundary using ultrasonic microscope to observe die bonding film and BGA substrate is peeling, and calculates the ratio (%) be peeling.Result is as shown in table 1.
(moisture-proof reflow soldering test (when carrying out after thermal treatment in 1 hour for 175 DEG C))
Die bonding film A ~ the F obtained in each embodiment and comparative example is pasted under the condition of 40 DEG C on the square semi-conductor chip of 5mm, be then installed on BGA substrate under temperature 120 DEG C, pressure 0.1MPa, the condition of 1 second time.Again with drying machine by it 150 DEG C of thermal treatments 1 hour, then implement the thermal treatment of 1 hour at 175 DEG C.Then, (TOWAPress company manufactures to use forming machine, マ ニ ュ ア Le プ レ ス Y-1), under the condition of forming temperature 175 DEG C, clamping pressure 184kN, transmission pressure 5kN, 120 seconds time, sealing resin GE-100 (Nitto Denko Corp's manufacture), carry out sealing process.Then, under temperature 85 DEG C, humidity 60%RH, the condition of 168 hours time, carry out moisture absorption operation, then by sample by carrying out the IR reflow ovens of temperature setting in the mode temperature of more than 260 DEG C kept 10 seconds.For 9 semiconductor elements, whether the boundary using ultrasonic microscope to observe die bonding film and BGA substrate is peeling, and calculates the ratio (%) be peeling.Result is as shown in table 1.
(result)
For the die bonding film of embodiment 1 ~ 4, even if when at high temperature heat-treating (at 120 DEG C at 10 hours or 175 DEG C 1 hour) for a long time after chip join, after the sealing process as operation after this, when observing the border of die bonding film and adherend, bubble (space) is also few.In addition, good result is also shown in humidity test.

Claims (9)

1. a die bonding film, wherein,
Containing nitrile group-containing thermoset acrylics analog copolymer and solidifying agent,
Use differential calorimeter, thermal discharge when measuring from 25 DEG C to 300 DEG C with the heat-up rate of 10 DEG C/min is below 10mJ/mg,
Described nitrile group-containing thermoset acrylics analog copolymer contains epoxy group(ing), and oxirane value is more than 0.1eq/kg and below 1eq/kg.
2. die bonding film as claimed in claim 1, is characterized in that,
With 175 DEG C of thermofixations after 5 hours for benchmark, the temperature of weightless 5 % by weight is more than 280 DEG C,
Be less than 1 % by weight at the water-intake rate of 175 DEG C of thermofixations after 5 hours.
3. die bonding film as claimed in claim 1, is characterized in that,
Stretching store elastic modulus at after 5 hours 260 DEG C of 175 DEG C of thermofixations is more than 0.5MPa.
4. die bonding film as claimed in claim 1, is characterized in that,
If when the weight of described nitrile group-containing thermoset acrylics analog copolymer is x, the weight of described solidifying agent is y, weight ratio (x/y) is more than 2 and less than 20.
5. die bonding film as claimed in claim 1, is characterized in that,
The weight-average molecular weight of described nitrile group-containing thermoset acrylics analog copolymer is more than 500,000.
6. die bonding film as claimed in claim 1, is characterized in that,
Described solidifying agent has phenolic hydroxyl group.
7. a dicing/die bonding film, is characterized in that,
Die bonding film according to claim 1 is layered on cutting film.
8. dicing/die bonding film as claimed in claim 7, is characterized in that,
Stretching store elastic modulus at 25 DEG C before the thermofixation of described die bonding film is more than 1MPa and below 5GPa.
9. a semiconductor device, is characterized in that,
Use the die bonding film according to any one of claim 1 to 6 or the dicing/die bonding film manufacture described in claim 7 or 8.
CN201510901642.3A 2011-08-03 2012-08-03 Chip bonding film, dicing chip bonding film, and semiconductor apparatus Pending CN105505244A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2011-170254 2011-08-03
JP2011170254A JP5930625B2 (en) 2011-08-03 2011-08-03 Die bond film, dicing die bond film, and semiconductor device
CN201210275227.8A CN102911616B (en) 2011-08-03 2012-08-03 Die bonding film, dicing/die bonding film and semiconductor device

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201210275227.8A Division CN102911616B (en) 2011-08-03 2012-08-03 Die bonding film, dicing/die bonding film and semiconductor device

Publications (1)

Publication Number Publication Date
CN105505244A true CN105505244A (en) 2016-04-20

Family

ID=47610204

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201510901642.3A Pending CN105505244A (en) 2011-08-03 2012-08-03 Chip bonding film, dicing chip bonding film, and semiconductor apparatus
CN201210275227.8A Active CN102911616B (en) 2011-08-03 2012-08-03 Die bonding film, dicing/die bonding film and semiconductor device

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201210275227.8A Active CN102911616B (en) 2011-08-03 2012-08-03 Die bonding film, dicing/die bonding film and semiconductor device

Country Status (3)

Country Link
JP (1) JP5930625B2 (en)
CN (2) CN105505244A (en)
TW (1) TWI552216B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6074357B2 (en) * 2013-12-24 2017-02-01 日東電工株式会社 Adhesive film, dicing die bond film, semiconductor device manufacturing method, and semiconductor device
JP6812212B2 (en) * 2016-11-14 2021-01-13 日東電工株式会社 Manufacturing methods for sheets, tapes and semiconductor devices
JP7019333B2 (en) * 2017-04-17 2022-02-15 日東電工株式会社 Dicing die bond film
JP7038575B2 (en) * 2018-03-08 2022-03-18 日東電工株式会社 Sealing sheet
JP7033003B2 (en) * 2018-05-23 2022-03-09 日東電工株式会社 Dicing die bond film
CN112234019B (en) * 2020-10-20 2023-01-17 广东省科学院半导体研究所 Transfer film, transfer assembly and micro device curved surface transfer method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101681845A (en) * 2007-06-22 2010-03-24 住友电木株式会社 Adhesive film and semiconductor device obtained with the same
CN101798490A (en) * 2009-02-06 2010-08-11 信越化学工业株式会社 Adhesive composite, adhesive sheet, cutting-die attach film and semiconductor device
CN102676093A (en) * 2011-03-11 2012-09-19 日东电工株式会社 Die-bonding film and use thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IE55238B1 (en) * 1983-08-03 1990-07-04 Nat Starch Chem Corp Carrier film with conductive adhesive for dicing of semiconductor wafers
JPH0616524B2 (en) * 1984-03-12 1994-03-02 日東電工株式会社 Adhesive thin plate for fixing semiconductor wafers
JP2009124135A (en) * 2007-10-24 2009-06-04 Hitachi Chem Co Ltd Adhesive member for semiconductor and semiconductor device
JP2010006912A (en) * 2008-06-25 2010-01-14 Shin-Etsu Chemical Co Ltd Adhesive composition, adhesive film, and dicing die attach film
JP4994429B2 (en) * 2008-08-04 2012-08-08 日東電工株式会社 Dicing die bond film
JP5143196B2 (en) * 2009-09-28 2013-02-13 日東電工株式会社 Film for semiconductor devices
JP4976481B2 (en) * 2009-12-04 2012-07-18 日東電工株式会社 Thermosetting die bond film, dicing die bond film, and semiconductor device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101681845A (en) * 2007-06-22 2010-03-24 住友电木株式会社 Adhesive film and semiconductor device obtained with the same
CN101798490A (en) * 2009-02-06 2010-08-11 信越化学工业株式会社 Adhesive composite, adhesive sheet, cutting-die attach film and semiconductor device
CN102676093A (en) * 2011-03-11 2012-09-19 日东电工株式会社 Die-bonding film and use thereof

Also Published As

Publication number Publication date
TW201308417A (en) 2013-02-16
CN102911616A (en) 2013-02-06
JP2013038097A (en) 2013-02-21
CN102911616B (en) 2016-01-20
TWI552216B (en) 2016-10-01
JP5930625B2 (en) 2016-06-08

Similar Documents

Publication Publication Date Title
CN102399505B (en) Dicing/die bonding film
CN102676093B (en) Die bonding film and uses thereof
CN102010677B (en) Thermosetting die bonding film, dicing/die bonding film and semiconductor device
CN102222633B (en) Thermosetting die bond film, dicing die bond film and method for manufacturing semiconductor device
CN102002323B (en) Adhesive film with dicing sheet and method of manufacturing the same
CN102190975B (en) Die bond film, dicing die bond film, and semiconductor device
CN102153956B (en) Heat curing-type adhesive foil, with the cutting adhesive foil of thin film and use the method that they manufacture semiconductor devices
CN101385135B (en) Process for producing semiconductor device
CN103140917B (en) Dicing/die bonding film and manufacturing method for semiconductor device
CN102911616B (en) Die bonding film, dicing/die bonding film and semiconductor device
CN102190977A (en) Dicing die-bonding film
KR101492629B1 (en) Adhesive composition, adhesive sheet and production process for semiconductor device
CN103081069B (en) Film for semiconductor apparatus and semiconductor device
CN102673076B (en) Cutting film with protective film
CN104946150A (en) Chip bonding film, chip bonding film with cutting sheet, semiconductor and making method thereof
CN104946151A (en) Chip bonding film, chip bonding film with cutting sheet, semiconductor device and making method thereof
JP4976481B2 (en) Thermosetting die bond film, dicing die bond film, and semiconductor device
CN104946152A (en) Cutting film, cutting/chip bonding film and semiconductor making method
CN103992755A (en) Film adhesive, dicing tape with film adhesive, method of manufacturing semiconductor device, and semiconductor device
CN105143344A (en) Thermosetting resin composition and semiconductor device manufacturing method
CN104212375B (en) Adhesive sheet and dicing/die bonding film
CN102190973A (en) Film for manufacturing semiconductor device and method of manufacturing semiconductor device
CN102911617A (en) Dicing die-bonding film
CN101857778A (en) Thermosetting die bonding film
CN104342047A (en) A chip engaging film with a cutting adhesive tape and a manufacturing method of a semiconductor device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20160420

RJ01 Rejection of invention patent application after publication