CN1847347A - Adhesive sheet for pfoducing semiconductor device, semiconductor device and method for manufacturing same - Google Patents

Adhesive sheet for pfoducing semiconductor device, semiconductor device and method for manufacturing same Download PDF

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Publication number
CN1847347A
CN1847347A CNA2006100664027A CN200610066402A CN1847347A CN 1847347 A CN1847347 A CN 1847347A CN A2006100664027 A CNA2006100664027 A CN A2006100664027A CN 200610066402 A CN200610066402 A CN 200610066402A CN 1847347 A CN1847347 A CN 1847347A
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Prior art keywords
semiconductor device
adhesive sheet
producing
resin
binder layer
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CNA2006100664027A
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CN100500784C (en
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佐藤健
桥本展宏
山井敦史
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Tomoegawa Co Ltd
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Tomoegawa Paper Co Ltd
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Abstract

The invention discloses a bonding film of semiconductor device, semiconductor device and preparing method, which is characterized by the following: the bonding film can inhibit silicon adhesive from gas overflowing, which maintains lead wire connecting and prevents glue remaining; the adhesive layer contains heat-solidifying resin part (a), heat-plastic resin part (b) and fluorine adhesive agent (c).

Description

Semiconductor device adhesive sheet for producing, semiconductor device and manufacture method thereof
Technical field
The present invention relates to semiconductor device adhesive sheet for producing, semiconductor device and manufacture method thereof.
The right of priority that Japanese patent application 2005-316560 number that the application advocates to submit on March 30th, 2005 Japanese patent application was submitted on October 31st, 2005-099481 number 1 and Japanese patent application are 2005-316561 number, its content quotation in this article.
Background technology
In recent years, follow miniaturization, the multifunction of electron devices such as portable type Personal Computer, Cell phone, except the electronic unit miniaturization that requires to constitute electron device, highly integrated, the High Density Packaging Technology of electronic unit also is necessary.Under this background, replace existing QFP (Quad Flat Package) and SOP peripheral encapsulation type semiconductor devices such as (Small Outline Package), but begin to be conceived to the so-called CSP face encapsulation type semiconductor devices such as (Chip Scale Package) of high density packing.And, because in CSP, particularly QFN (Quad FlatNon-leaded) can adopt existing semiconductor device manufacturing technology to make, and therefore is mainly used in the following few terminal semiconductor device of 100 pins (pin) or 100 pins.
As the manufacture method of QFN, known following method.
At first, at a side surface applying adhesive sheet (adhesive sheet bonding process) of lead frame, semiconductor elements (chip adhesive (die attach) operation) such as IC chip are carried respectively in a plurality of mounting semiconductor element portions (chip carrier (die pad) portion) that form on lead frame.Then, a plurality of leads and the semiconductor element that will set along the periphery of each semiconductor element equipped section of lead frame is electrically connected (wire-bonded (wire bonding) operation) by bonding wire (bonding wire).Next, with the semiconductor element (resin package operation) of potting resin encapsulation lift-launch on lead frame.Adhesive sheet is peeled off (adhesive sheet stripping process) from lead frame, thereby can form the QFN unit that is arranged with a plurality of QFN.At last, the cutting of QFN unit is come (cutting action), make a plurality of QFN thus simultaneously along the periphery of each QFN.
The spy opens in 2002-184801 communique and the special manufacture method of opening the QFN in the 2000-294579 communique and utilizes the adhesive sheet that has used silicon class tackiness agent or acrylic adhesives.But, when using silicon class tackiness agent or acrylic adhesives, result from the flash (mould flash) of tackiness agent sometimes.In addition, sometimes because of the tackiness agent generation evolving gas composition of heating by adhesive sheet.This evolving gas composition causes sometimes that attached to leadframe surfaces the joint of bonding wire is bad.In addition, the adaptation that also may cause lead frame and potting resin reduces.Thereby the yield rate that semiconductor device is made reduces, reliability reduces.
In order to improve the problems referred to above, the spy opens the self adhesive tape that has proposed to use heat-curing type adhesive in the 2003-336015 communique.
Summary of the invention
Usually, before the wire-bonded operation, implement plasma and clean, remove impurity, further improve the wire-bonded characteristic attached to the surface.
But, when adopt to use going up the existing semiconductor device adhesive sheet for producing of note heat-curing type adhesive, alligatoring is cleaned because of plasma in the face top layer of exposing of adhesive sheet, when stripping semiconductor is used adhesive sheet, tackiness agent might take place move to splicing ear, the potting resin face (hereinafter referred to as " glue is residual ") of semiconductor device.If it is residual that above-mentioned glue takes place, then adhesive attachment may cause the semiconductor device generation poor flow of making by the part of potting resin encapsulation or be positioned at the external connection terminals of its lead-in wire that closely is close to.
The invention solves above-mentioned problem, its purpose is to provide a kind of semiconductor device adhesive sheet for producing, semiconductor device and manufacture method thereof, above-mentioned semiconductor device adhesive sheet for producing suppresses because of using the generation of the evolving gas composition that silicon class tackiness agent etc. produces, simultaneously when being used for the manufacturing of semiconductor devices such as QFN, the good wire-bonded and the flash characteristic that can the maintenance heat curing adhesive have, prevent that simultaneously glue is residual, thereby can prevent the defective productsization of semiconductor device.
In addition, its purpose also is to provide a kind of semiconductor device adhesive sheet for producing, plasma cleans even this semiconductor device adhesive sheet for producing is not implemented before the wire-bonded operation, the wire-bonded characteristic is also good, the semiconductor device that the adaptation that can obtain lead frame and potting resin is good, reliability is good.
The present invention to achieve these goals, the first semiconductor device adhesive sheet for producing is provided, be strippingly to be fitted in the lead frame of semiconductor device or the semiconductor device adhesive sheet for producing on the wiring substrate, it is characterized by, possess base material and binder layer, above-mentioned binder layer contains thermosetting resin composition (a), thermoplastic resin composition (b) and fluorine class additive (c).
Above-mentioned first semiconductor device is used in the adhesive sheet, the compound more than a kind or a kind that above-mentioned fluorine class additive (c) is preferably selected from fluorine-containing graftomer, fluorinated block copolymer and fluorine-containing aliphatic category polymer esters.
In addition, the present invention to achieve these goals, the second semiconductor device adhesive sheet for producing is provided, be strippingly to be fitted in the lead frame of semiconductor device or the semiconductor device adhesive sheet for producing on the wiring substrate, it is characterized by, possess base material and binder layer, above-mentioned binder layer contains fluoro-resin.
Above-mentioned second semiconductor device is with in the adhesive sheet, preferably: above-mentioned binder layer contains thermosetting resin composition (a1) and thermoplastic resin composition (b1), and any in this thermosetting resin composition (a1) and the thermoplastic resin composition (b1) is fluorine-containing olefine kind resin.
The thermosetting resin composition (a1) of above-mentioned binder layer and the mass ratio (a1)/(b1) of thermoplastic resin composition (b1) are preferably 0.05～0.43.
The quality molecular-weight average of thermoplastic resin composition (b1) also is preferably 2,000～1,000,000.
Storage modulus after above-mentioned binder layer solidifies also is preferably 0.1MPa or more than the 0.1MPa in the time of 150～250 ℃.
Binder layer after the curing also is preferably 0.03～5N/cm 150～200 ℃ bond strength.
In addition, above-mentioned base material preferred glass temperature is more than 150 ℃ or 150 ℃, thermal expansivity is 5～50ppm/ ℃ thermotolerance film.
The also preferred thermal expansivity of above-mentioned base material is 5～50ppm/ ℃ a tinsel.
And, the present invention to achieve these goals, the 3rd semiconductor device adhesive sheet for producing is provided, be strippingly to be fitted in the lead frame of semiconductor device or the semiconductor device adhesive sheet for producing on the wiring substrate, it is characterized by, possess base material and binder layer, above-mentioned binder layer contains fluoro-resin and reactive elastomerics.
In above-mentioned the 3rd semiconductor device adhesive sheet for producing, above-mentioned fluoro-resin preferably contains the multipolymer that the raw material monomer of fluoroolefin and vinyl ether is polymerized and/or contains fluoroolefin and multipolymer that the raw material monomer of vinyl ester is polymerized.
Above-mentioned reactive elastomerics also is preferably the styrene-ethylene-butylene copolymer that contains maleic anhydride.
In above-mentioned first～the 3rd semiconductor device adhesive sheet for producing, preferably the single face at binder layer is provided with protective membrane.
The present invention provides a kind of semiconductor device to achieve these goals, it is characterized by, and this semiconductor device is to use above-mentioned first～the 3rd semiconductor device adhesive sheet for producing to make.
The present invention provides a kind of manufacture method of semiconductor device to achieve these goals, it is characterized by, and this method uses above-mentioned first～the 3rd semiconductor device adhesive sheet for producing to make.
Need to prove, comprise the compound that the hydrogen atom of alkene is partly or entirely replaced by fluorine atom in the definition of " fluoroolefin " in present specification and the claim.For example, the hydrogen atom of the compound that partly or entirely replaced by fluorine atom of the hydrogen atom that comprises alkene and alkene by fluorine atom replace, the definition of residual hydrogen atomic component or the compound that all replaced by other atoms such as chlorine atoms simultaneously.
In addition, " fluoro-resin " broad sense is the resin that comprises fluorine atom.
In the resin package operation that is used for making semiconductor device, the limit is heated to 150～200 ℃, and the limit applies the pressure of 5～10GPa, utilizes resin package, packaging semiconductor.Therefore, it is that the bounding force (bond strength of binder layer and lead frame) of binder layer reduces that the binder layer of adhesive sheet is exposed to result in the high temperature, and under the pressure of potting resin, binder layer is peeled off from lead frame top, and flash takes place.But therefore the problems referred to above do not take place because the bounding force of binder layer does not further reduce in adhesive sheet of the present invention.
The present invention can suppress because of using the generation of the evolving gas composition that silicon class tackiness agent etc. produces, simultaneously when being used to make semiconductor device such as QFN, the good wire-bonded and the flash characteristic that can the maintenance heat curing adhesive have prevent that simultaneously glue is residual.Thereby can provide semiconductor device adhesive sheet for producing, semiconductor device and the manufacture method thereof that can prevent the semiconductor device defective productsization.
In addition, a kind of semiconductor device adhesive sheet for producing can be provided, even not implementing plasma before the wire-bonded operation, do not clean this semiconductor device adhesive sheet for producing, the wire-bonded characteristic is also good, the semiconductor device that the adaptation that can obtain lead frame and potting resin is good, reliability is good.
In addition, before the wire-bonded operation, binder layer is implemented plasma and clean and also can keep suitable separability, the residual semiconductor device adhesive sheet for producing of glue does not take place even the present invention can provide a kind of.
Description of drawings
The plane sketch of one of the lead frame that Fig. 1 preferably uses when using semiconductor device adhesive sheet for producing of the present invention to make QFN example.
Fig. 2 provides manufacturing process's example of QFN, is the A-A ' sectional view of Fig. 1.
Drawing reference numeral
10 semiconductor device adhesive sheet for producing
20 lead frames
30 semiconductor elements
31 bonding wires
40 potting resins
Embodiment
Describe the present invention below in detail.
Adhesive sheet of the present invention is strippingly to be fitted in the lead frame of semiconductor device or the thin slice on the wiring substrate.Herein, lead frame is meant the part that forms conductive pattern by etching or pressurized metal plate etc., and wiring substrate is meant that (also comprising internal surface sometimes) on the surface of electrical insulating property substrate forms conductive pattern with conductive material, and it is solidified and the bonding substrate that obtains.
Need to prove in the following description,, lead frame is described as the applying object, but wiring substrate also is same for the ease of understanding.
Adhesive sheet of the present invention has base material and binder layer.
As base material, can enumerate and have stable on heating base material, for example heat-resistant resin film or tinsel etc.
When using adhesive sheet of the present invention to make semiconductor device such as QFN, adhesive sheet is exposed in chip adhesive operation, wire-bonded operation, resin package operation in 150～250 ℃ the high temperature, when using heat-resistant resin film as base material, if temperature reaches more than the second-order transition temperature (Tg), then the thermal expansivity of heat-resistant resin film will sharply increase, the thermal expansion difference of itself and metal making wire frame is increased, therefore, when recovering room temperature, warpage might take place in thermotolerance film and lead frame.Thus, when thermotolerance film and lead frame generation warpage, in the resin package operation, might can't be on the dowel pins of model with leadframe package, thus cause position deviation.
Therefore, when using the thermotolerance film as base material, the preferred glass temperature is the thermotolerance film more than 150 ℃ or 150 ℃, is preferably especially more than 180 ℃ or 180 ℃.
The thermal expansivity of heat-resistant resin film in the time of 150～250 ℃ is preferably 5～50ppm/ ℃, more preferably 10～30ppm/ ℃.Thermotolerance film as having above-mentioned characteristic can list the film that is made of polyimide, polymeric amide, polyethersulfone, polyphenylene sulfide, polyetherketone, polyether-ether-ketone, tri acetyl cellulose, polyetherimide etc.
When using tinsel as base material, based on the identical reason of above-mentioned thermotolerance film, also require the thermal expansivity of tinsel in the time of 150～250 ℃ to be preferably 5～50ppm/ ℃, more preferably 10～30ppm/ ℃.As metal, can list the paper tinsel that constitutes by gold and silver, copper, platinum, aluminium, magnesium, titanium, chromium, manganese, iron, cobalt, nickel, zinc, palladium, cadmium, indium, tin, lead etc., and be the Alloy Foil of principal constituent or their anodized foil etc. with above-mentioned metal.
In addition, when using adhesive sheet of the present invention to make semiconductor device, residual in order to prevent that glue takes place in the adhesive sheet stripping process, the bond strength Sa of base material and binder layer and ratio (bond strength ratio) Sa/Sb of the bond strength Sb of potting resin and lead frame and binder layer are preferably more than 1.5 or 1.5.When Sa/Sb less than 1.5, it is residual, therefore not preferred that glue takes place in the adhesive sheet stripping process easily.What should illustrate is to be more than 1.5 or 1.5 in order to make bond strength than Sa/Sb, at base material is under the situation of thermotolerance film, preferably before forming binder layer, in advance a side surface of the formation binder layer of thermotolerance film is implemented the processing that Corona discharge Treatment, plasma treatment, primary coat processing, sandblasting etc. are used to improve the bond strength Sa of thermotolerance film and binder layer.In addition, tinsel can be divided into extruded metal paper tinsel and electrolytic metal paper tinsel by its method for making, is more than 1.5 or 1.5 in order to make bond strength than Sa/Sb, when using the electrolytic metal paper tinsel, preferably on a side surface of asperitiesization binder layer is set.And, in the electrolytic metal paper tinsel, also especially preferably use electrolytic copper foil.
In addition, make binder layer be solidificated on the lead frame after bond strength in the time of 150～200 ℃ be that 0.03～5N/cm can prevent flash, therefore preferred.If reach 0.03N/cm or more than the 0.03N/cm, then be difficult for taking place flash; If be 5N/cm or below the 5N/cm, it is residual to be difficult for that then glue takes place.In addition, consider that preferably making the uncured normal temperature adhesive intensity on lead frame time of binder layer is 0.98N/cm or more than the 0.98N/cm from the manufacturing process aspect.Its reason is that bond strength reaches 0.98N/cm or 0.98N/cm when above, and during transporting in the manufacturing process, binder layer is difficult for peeling off from lead frame.Need to prove that detailed measuring method is following
Describe among the embodiment.
Below, the binder layer that the first semiconductor device adhesive sheet for producing of the present invention possesses is described.
The binder layer that the first semiconductor device adhesive sheet for producing of the present invention possesses contains thermosetting resin composition (a) and the thermoplastic resin composition (b) that constitutes tackiness agent base material [principal constituent (matrix)], also contains fluoride additive (c).Promptly, binder layer must contain fluorine class additive (c), also contain and different thermosetting resin composition (a) and the thermoplastic resin compositions (b) of fluorine class additive (c) kind (chemical structure or molecular weight etc.), thereby must constitute more than the composition by 3 kinds of compositions or 3 kinds.
The total amount of thermosetting resin composition (a) and thermoplastic resin composition (b) in binder layer 1 00 mass parts, reach 95 mass parts or more than 95 mass parts, be preferably 97～99.9 mass parts.Total amount is a lower value or more than the lower value, can fully obtain the function as binder layer.
The mass ratio (a)/(b) of thermosetting resin composition (a) and thermoplastic resin composition (b) is preferably 0.05～2, more preferably 0.3～1.6.Make (a)/(b) in above-mentioned scope, both balances are good, can obtain to improve the effect of the detached from each other or cohesive force of composition.
Need to prove that thermosetting resin composition (a) and/or thermoplastic resin composition (b) also can contain fluoro-resin.At this moment,, then contain the resinous principle of fluorine and when making coating, do not separate, can easily form binder layer with the resinous principle that does not contain fluorine if (a)/(b) be below 2 or 2.If (a)/(b) be more than 0.05 or 0.05, then the cohesive force of binder layer does not reduce, and is difficult for taking place flash in the resin package operation.
Thermosetting resin composition (a)
As thermosetting resin composition (a), can enumerate urea resin, melamine resin, benzoguanamine resin, acetylguanamine resin, resol, resorcinol resin, xylene resin, furane resin, unsaturated polyester resin, diallyl phthalate ester resin, isocyanate resin, Resins, epoxy, maleimide resin, nadic acid imide (nadiimide) resin etc.Above-mentioned resin can use a kind separately, also can be also with more than 2 kinds or 2 kinds.
In order to obtain preferably in above-mentioned thermosetting resin, also containing at least a kind in Resins, epoxy and the resol having high elastic coefficient under the treatment temp of wire-bonded operation, under the treatment temp of resin package operation, also can keeping and the binder layer of the high bond strength of lead frame simultaneously.
(a) also can use fluoro-resin as the thermosetting resin composition.Be different from as fluorine class additive (c) that must composition as the chemical structure of the fluoro-resin of thermosetting resin composition (a), addition is also different.
For thermosetting resin composition (a), as fluoro-resin, can enumerate at urea resin, melamine resin, benzoguanamine resin, the acetylguanamine resin, resol, resorcinol resin, xylene resin, furane resin, unsaturated polyester resin, diallyl phthalate ester resin, isocyanate resin, Resins, epoxy, maleimide resin, import the resin that fluorine obtains in the thermosetting resin compositions such as nadic acid imide resin, or at vinylidene fluoride, R 1216, tetrafluoroethylene, the monomer that has functional group's (reactive group) in the olefine kind resins such as perfluoro methyl vinyl ether overlaps the multipolymer form or the multipolymer that combines more than 2 kinds or 2 kinds in the above-claimed cpd etc.And, also can be for adding the multipolymer that ethene or coincidences such as propylene, alkyl vinyl ether form.Wherein, particularly owing to have the resinoid fluorine content of Fluorine containing olefine of functional group patience height many, that the plasma before the wire-bonded is cleaned, so more preferred.
And, particularly, can enumerate following fluoro-resin, this fluoro-resin is to contain the multipolymer that the monomeric raw material monomer of hydro carbons such as fluoroolefin and vinyl ether, vinyl ester is polymerized and have functional groups such as hydroxyl, carboxyl, epoxy group(ing).
Fluoro-resin with above-mentioned functional group for example can cooperate the monomer with functional group in the above-mentioned raw materials monomer, make its copolymerization and obtain.In addition, also can have the fluoro-resin of unsaturated link(age) such as vinyl in preparation after, in above-mentioned unsaturated link(age), import functional group such as epoxy group(ing) and obtain.
As monomer, for example can enumerate the monomer that vinylformic acid, methacrylic acid etc. have ethylenic linkage and functional group with functional group.
As above-mentioned fluoro-resin, various production marketings are arranged.
Wherein, particularly residual, peelable in order to prevent the casting resin leakage and not have glue, preferred following fluoro-resin, this fluoro-resin is to contain the multipolymer that the raw material monomer of fluoroolefin and vinyl ether is polymerized and/or contain fluoroolefin and multipolymer that the raw material monomer of vinyl ester is polymerized, and has functional groups such as hydroxyl, carboxyl, epoxy group(ing).
As more preferably routine, particularly, can enumerate following resin:
This resin is by trifluoro-ethylene and is selected from cyclohexyl vinyl ether, alkyl vinyl ether, reaches the multipolymer that monomer copolymerization forms more than a kind or a kind of hydroxyalkyl vinyl ether and has functional group;
This resin is by trifluoro-ethylene and is selected from the multipolymer that monomer copolymerization forms more than a kind or a kind of alkyl vinyl ether and allyl alcohol and has functional group;
This resin is by trifluoro-ethylene and is selected from the aliphatic carboxylic acid vinyl ester, reaches the multipolymer that monomer copolymerization forms more than a kind or a kind of hydroxyalkyl vinyl ester and has functional group.
Wherein, for example can enumerate vinyl fluoride vinyl ether co-polymer (system trade(brand)name: the Lumiflon of Asahi Glass society with functional group as commercially available product; Functional group is hydroxyl or carboxyl) etc.
When containing the above fluoro-resin of enumerating, its content is 5～40 mass parts, is preferably 20～30 mass parts with respect to binder layer 100 mass parts.By making content reach 5 mass parts or more than 5 mass parts, can making separability become more good, more difficult generation glue is residual.In addition, be 40 mass parts or below 40 mass parts by making content, improved the intermiscibility with other resinous principles, help making.
Thermoplastic resin composition (b)
As thermoplastic resin composition (b), can enumerate acrylonitrile butadiene copolymer (NBR), acrylonitrile-butadiene-styrene resin (ABS), styrene butadiene-ethenoid resin (SEBS), styrene-butadiene-styrene resin (SBS), polyhutadiene, polyacrylonitrile, polyvinyl butyral acetal, polymeric amide, polyamidoimide, polyimide, polyester, urethane, acrylic rubber etc.Above-mentioned thermoplastic resin can only use a kind, also can be used in combination.
Can in thermoplastic resin composition (b), cooperate fluoro-resin.As the fluoro-resin that is engaged in the thermoplastic resin composition (b), can enumerate at acrylonitrile butadiene copolymer (NBR), acrylonitrile-butadiene-styrene resin (ABS), styrene butadiene-ethenoid resin (SEBS), styrene-butadiene-styrene resin (SBS), styrene-ethylene-butylene resin, polyhutadiene, polyacrylonitrile, polyvinyl butyral acetal, polymeric amide, polyamidoimide, polyimide, polyester, urethane, import the compound that fluorine obtains in the thermoplastic resin compositions such as acrylic rubber, or vinylidene fluoride, R 1216, tetrafluoroethylene, the polymkeric substance of olefine kind resins such as perfluoro methyl vinyl ether, or the multipolymer that combines more than 2 kinds or 2 kinds in the above-claimed cpd.And, also can be for having added the multipolymer of ethene or propylene, alkyl vinyl ether etc.The special material that is obtained by olefine kind resin can increase fluorine adding content, improves the weather resistance that the plasma before the wire-bonded is cleaned, and is therefore more preferred.
More specifically, can enumerate fluoroolefin and contain the multipolymer that the monomeric raw material monomers of hydro carbons such as vinyl ether, vinyl ester are polymerized.
Wherein, in order to prevent that casting resin from leaking and not have glue residual, peelable, especially preferably contain the multipolymer that the raw material monomer of fluoroolefin and vinyl ether is polymerized and/or contain fluoroolefin and multipolymer that the raw material monomer of vinyl ester is polymerized.
As more preferably example, particularly, can enumerate trifluoro-ethylene and be selected from the multipolymer that monomer copolymerization forms more than a kind or a kind of cyclohexyl vinyl ether, alkyl vinyl ether and hydroxyalkyl vinyl ether;
Trifluoro-ethylene and be selected from alkyl vinyl ether and the multipolymer that monomer copolymerization forms more than a kind or a kind of allyl alcohol;
Trifluoro-ethylene and be selected from aliphatic carboxylic acid vinyl ester, and the multipolymer that monomer copolymerization forms more than a kind or a kind of hydroxyalkyl vinyl ester etc.
When containing fluoro-resin in the thermoplastic resin composition (b), with respect to binder layer 100 mass parts, its content is 5～40 mass parts, be preferably 20～30 mass parts.By making its content reach 5 mass parts or more than 5 mass parts, can making separability become more good, more difficult generation glue is residual.In addition, be 40 mass parts or below 40 mass parts by making its content, can make the intermiscibility of itself and other resinous principle become more good, help making.
In addition, if in thermoplastic resin composition (b) the complex reaction elastomerics, then can improve effect of the present invention, thereby preferred.
As reactive elastomerics, can enumerate because of having functional groups such as carboxyl, amino, vinyl, epoxy group(ing) or having reactive elastic resin by anhydride monomers deutero-structural units such as maleic anhydrides.
Reactive elastomerics can make monomer with functional group or anhydride monomers copolymerization and make when the preparation elastic resin.In addition, can have the elastic resin of unsaturated link(age) such as ethylenic linkage in preparation after, make by in above-mentioned unsaturated link(age), importing functional groups such as epoxy group(ing).Need to prove,, for example can enumerate the monomer that vinylformic acid, methacrylic acid etc. have ethylenic linkage and functional group as monomer with functional group.
Particularly, can enumerate carboxylic styrene-butadiene copolymer, carboxylic styrene-isoprene multipolymer, carboxylic styrene butadiene saturated copolymer, carboxylic styrene-isoprene saturated copolymer, carboxylic styrene-ethylene-butylene-styrene multipolymer, carboxylic styrene-ethylene-butylene-styrene saturated copolymer, carboxylic acrylonitrile butadiene copolymer, amino modified polyol resin, amino modified phenoxy resin, amino modified acrylonitrile butadiene copolymer, polyvinyl butyral resin, polyvinyl acetal resin, carboxylic acrylonitrile butadiene copolymer, the acrylonitrile butadiene copolymer that contains the hydrogenation carboxyl, carboxylic acrylic rubber, the styrene-butadiene copolymer that contains maleic anhydride, the styrene-ethylene-butylene-styrene multipolymer that contains maleic anhydride, the saturated copolymer polyester resin of C-terminal, the saturated copolymer polyester resin of C-terminal, the styrenic block copolymer that contains epoxy group(ing), contain the styrene-ethylene-butylene copolymer of maleic anhydride etc.Above-mentioned reactive elastomerics can use a kind, or uses mixing more than 2 kinds or 2 kinds.Need to prove " containing maleic anhydride " expression and maleic anhydride copolymerization.
Wherein, as commercially available product, can enumerate following products.
As containing carboxylated acrylonitrile-butadienecopolymer, can enumerate Japanese ZEON society system trade(brand)name: Nipol 1072J, with society's system trade(brand)name: Nipol DN631, emerging products society of space portion system trade(brand)name: Hycar CTBN, JSR society makes trade(brand)name: PNR-1H etc.
As containing amino acrylonitrile butadiene copolymer, can enumerate system trade(brand)name: the Hycar ATBN etc. of emerging product society of space portion.
As the styrene-ethylene-butylene copolymer that contains maleic anhydride, can enumerate society of Asahi Chemical Industry system trade(brand)name: Tuftec M series product etc.
As the styrenic block copolymer that contains epoxy group(ing), can enumerate system trade(brand)name: the Epofriend etc. of DAICEL chemical industry society.
Wherein, in order to prevent that casting resin from leaking and not have glue residual, peelable, especially preferably contain the styrene-ethylene-butylene copolymer of maleic anhydride.In this multipolymer, maleic anhydride: vinylbenzene: the mass ratio of ethene-butylene (summation of ethene-butylene) is preferably 0.3～3: 10～40: 60～90, be preferably 0.5～1: 20～30: 70～80 especially.
With respect to binder layer 100 mass parts, reactive elastomeric usage quantity preferably in the scope of 30～95 mass parts, 40～90 mass parts more preferably.Usage quantity is 30 mass parts or 30 mass parts when above, be difficult for that flash takes place or glue residual.Usage quantity is 95 mass parts or 95 mass parts when following, and separability further improves, and more difficult generation glue is residual.
The quality molecular-weight average of thermoplastic resin composition (b) is 2,000～1,000,000, is preferably 5,000～800,000, more preferably 10,000～500,000 o'clock, can improve the cohesive force of binder layer, prevent that further the glue that takes place in the adhesive sheet stripping process is residual.
Fluorine class additive (c)
Fluorine class additive (c) preferred resin (also can be oligopolymer) can be enumerated fluorine-containing graftomer, fluorinated block copolymer, fluorine-containing aliphatic category polymer esters etc.Fluorine class additive (c) can use a kind, or uses mixing more than 2 kinds or 2 kinds.Above-mentioned additive preferred thermoplastic resin.
As fluorine-containing graftomer, can enumerate as fluorine-containing class graftomer comprehensive and grind chemical system trade(brand)name: the CHEMTREE LF-700 etc. of society.Need to prove that fluorine-containing class graftomer constitutes by dry polymeric with by a plurality of the polymkeric substance that described dry polymeric stretches out, dry polymeric is made of acrylic polymers, and the branch polymkeric substance is made of fluorine-containing polymkeric substance.
As fluorinated block copolymer, the segmented copolymer that is made of polymer segments that contains fluorinated alkyl and acrylic polymers fragment is with Japanese grease society system trade(brand)name: Modiper F series product, for example Modiper F200, Modiper F220, Modiper F2020, ModiperF3035, Modiper F600 sell.
In addition,, preferably have material, can enumerate system trade(brand)name: the Novec FC-4430 etc. of 3M society as the characteristic of nonionogenic tenside as fluorine-containing aliphatic category polymer esters.
Wherein, residual, peelable in order to prevent the casting resin leakage and not have glue, preferred especially fluorine-containing graftomer or fluorinated block copolymer.
With respect to binder layer 100 mass parts, the use level of fluorine class additive (c) is preferably 0.1～5 mass parts, 0.5～3 mass parts more preferably.By being lower value or more than the lower value, can improving effect of the present invention.Consider and the balance of material that constitutes the binder layer base material or saturated, the economy of effect, preferably be higher limit or below the higher limit.
In addition, for the thermal expansivity of adjusting binder layer, thermal conductivity, surface viscosity, binding property etc., preferably in binder layer, add inorganic or organic filler.Herein, as mineral filler, can list the filler that constitutes by crush type silicon-dioxide, fusion silicon-dioxide, aluminum oxide, titanium oxide, beryllium oxide, magnesium oxide, lime carbonate, titanium nitride, silicon nitride, boron nitride, titanium boride, tungsten boride, silicon carbide, titanium carbide, zirconium carbide, molybdenum carbide, mica, zinc oxide, carbon black, aluminium hydroxide, calcium hydroxide, magnesium hydroxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT etc., or in their surface, import trimethylsiloxy etc. and the filler of formation.As organic filler, can list the filler that constitutes by polyimide, polyamidoimide, polyether-ether-ketone, polyetherimide, polyester-imide, nylon, silicone resin etc.
The following describes the bonding coat that the second semiconductor device adhesive sheet for producing possesses.
Binder layer of the present invention contains fluoro-resin.Herein, fluoro-resin is described as described above for containing the resin of fluorine element as constituent.
Binder layer contains thermosetting resin composition (a1) and thermoplastic resin composition (b1), and it is comparatively desirable that any in thermosetting resin composition (a1) or the thermoplastic resin composition (b1) contains fluoro-resin.At this moment, the mass ratio (a1)/(b1) of thermosetting resin composition (a1) and thermoplastic resin composition (b1) is preferably 0.05～0.43, more preferably 0.11～0.25.
If (a1)/(b1) be below 0.43 or 0.43, the resinous principle that then contains the resinous principle of fluorine and do not contain fluorine is not easily separated when making coating, form binder layer easily.(a1)/(b1) be 0.05 or 0.05 when above, the cohesive force of binder layer is difficult for reducing, so is difficult for taking place flash in the resin package operation.
Thermosetting resin composition (a1)
As thermosetting resin composition (a1), can enumerate urea resin, melamine resin, benzoguanamine resin, acetylguanamine resin, resol, resorcinol resin, xylene resin, furane resin, unsaturated polyester resin, diallyl phthalate ester resin, isocyanate resin, Resins, epoxy, maleimide resin, nadic acid imide resin etc.Above-mentioned resin can use separately, also can be also with more than 2 kinds or 2 kinds.By containing at least a kind in Resins, epoxy and the resol therein, can access have high elastic coefficient under the treatment temp of wire-bonded operation and under the treatment temp of resin package operation the binder layer high with the bond strength of lead frame, be preferred therefore.
In addition, also can will contain the thermosetting resin composition of fluorine as above-mentioned thermosetting resin composition (a1).As the thermosetting resin composition that contains fluorine, can enumerate and in above-mentioned thermosetting resin composition, imported the material of fluorine or contained the polymer of monomers that in olefine kind resins such as vinylidene fluoride, R 1216, tetrafluoroethylene, perfluoro methyl vinyl ether, has reactive functional groups or the multipolymer that combines more than 2 kinds or 2 kinds in the above-mentioned substance etc.And, also can be for having added the multipolymer of ethene or propylene, alkyl vinyl ether etc.Wherein, particularly because the resinoid fluorine content of Fluorine containing olefine is many, patience height that the plasma before the wire-bonded is cleaned, so more preferred.
Thermoplastic resin composition (b1)
As thermoplastic resin composition (b1), can enumerate acrylonitrile butadiene copolymer (NBR), acrylonitrile-butadiene-styrene resin (ABS), styrene butadiene-ethenoid resin (SEBS), styrene-butadiene-styrene resin (SBS), polyhutadiene, polyacrylonitrile, polyvinyl butyral acetal, polymeric amide, polyamidoimide, polyimide, polyester, urethane, acrylic rubber etc.Above-mentioned resin can use separately, also can be also with more than 2 kinds or 2 kinds.
In addition, also can will contain the thermoplastic resin of fluorine as above-mentioned thermoplastic resin composition (b1).As the thermoplastic resin composition that contains fluorine, can enumerate the material that in above-mentioned thermoplastic resin composition, has imported fluorine, as olefine kind resin, can enumerate vinylidene fluoride, R 1216, tetrafluoroethylene, perfluoro methyl vinyl ether etc. polymkeric substance or, the multipolymer that combines more than 2 kinds or 2 kinds.And, also can be for having added the multipolymer of ethene or propylene, alkyl vinyl ether etc.Wherein, particularly since the material that contains olefine kind resin make fluorine content increase, to the weather resistance height that the plasma before the wire-bonded cleans, therefore more preferred.
The quality molecular-weight average of thermoplastic resin composition (b1) is 2,000～1,000,000, is preferably 5,000～800,000, more preferably 10,000～500,000 o'clock, can improve the cohesive force of binder layer, prevent that further the glue that takes place in the adhesive sheet stripping process is residual.
In addition, the bonding coat that the binder layer that second adhesive sheet possesses also can possess with first adhesive sheet preferably adds inorganic or organic filler similarly in order to adjust thermal expansivity, thermal conductivity, surface viscosity, binding property etc. in binder layer.
The following describes the bonding coat that the 3rd semiconductor device adhesive sheet for producing possesses.
The bonding coat that the 3rd semiconductor device adhesive sheet for producing of the present invention possesses contains fluoro-resin and reactive elastomerics.Herein, described as described above being meant of fluoro-resin contained the resin of fluorine element as constituent.
(fluoro-resin)
As above-mentioned fluoro-resin, can enumerate and contain polymkeric substance that (copolymerization) have functional group's (reactive group) in olefine kind resins such as vinylidene fluoride, R 1216, tetrafluoroethylene, perfluoro methyl vinyl ether monomer obtains or the multipolymer that combines more than 2 kinds or 2 kinds in the above-mentioned substance etc.And, also can be for adding the multipolymer that ethene or coincidences such as propylene, alkyl vinyl ether form.Wherein, particularly owing to have the resinoid fluorine content of Fluorine containing olefine of functional group patience height many, that the plasma before the wire-bonded is cleaned, so more preferred.
And, particularly, can enumerate following fluoro-resin, this fluoro-resin is to contain the multipolymer that the monomeric raw material monomer of hydro carbons such as fluoroolefin and vinyl ether, vinyl ester is polymerized and have functional groups such as hydroxyl, carboxyl, epoxy group(ing).
Fluoro-resin with above-mentioned functional group for example can except above-mentioned monomer, also cooperate the monomer with functional group in starting monomer, make its copolymerization and make.In addition, also can have the fluoro-resin of unsaturated link(age) such as vinyl in preparation after, in unsaturated link(age)s such as above-mentioned vinyl, import functional group such as epoxy group(ing) and make.
As monomer, for example can enumerate the monomer that vinylformic acid, methacrylic acid etc. have ethylenic linkage and functional group with functional group.
As above-mentioned fluoro-resin, various production marketings are arranged.
Wherein, residual, peelable in order to prevent the casting resin leakage and not have glue, preferred especially following fluoro-resin, this fluoro-resin are to contain the multipolymer that the raw material monomer of fluoroolefin and vinyl ether is polymerized and/or contain fluoroolefin and multipolymer that the raw material monomer of vinyl ester is polymerized and have functional groups such as hydroxyl, carboxyl, epoxy group(ing).
As more preferably routine, particularly, can enumerate following resin:
This resin is trifluoro-ethylene and is selected from the multipolymer that monomer copolymerization forms more than a kind or a kind of cyclohexyl vinyl ether, alkyl vinyl ether and hydroxyalkyl vinyl ether and has functional group;
This resin is trifluoro-ethylene and is selected from alkyl vinyl ether and the multipolymer that monomer copolymerization forms more than a kind or a kind of allyl alcohol and have functional group;
This resin is trifluoro-ethylene and is selected from the aliphatic carboxylic acid vinyl ester, reaches the multipolymer that monomer copolymerization forms more than a kind or a kind of hydroxyalkyl vinyl ester and has functional group.
Wherein, as commercially available product, for example can enumerate vinyl fluoride vinyl ether co-polymer (system trade(brand)name: the Lumiflon of Asahi Glass society with functional group; Functional group is hydroxyl or carboxyl) etc.
With respect to binder layer 100 mass parts, the use level of the above-mentioned fluoro-resin of enumerating is preferably 5～40 mass parts, 20～30 mass parts more preferably.By making use level is 5 mass parts or more than 5 mass parts, can further improve separability, prevent that glue is residual.In addition, be 40 mass parts or below 40 mass parts by making use level, can improve the intermiscibility with other resinous principles, help making.
(reactive elastomerics)
As reactive elastomerics, can enumerate because of having functional groups such as carboxyl, amino, vinyl, epoxy group(ing) or having reactive elastic resin by anhydride monomers deutero-structural units such as maleic anhydrides.
Reactive elastomerics can make monomer with functional group or anhydride monomers copolymerization and make when the preparation elastic resin.In addition, can have the elastic resin of unsaturated link(age) such as ethylenic linkage in preparation after, make by in above-mentioned unsaturated link(age), importing functional groups such as epoxy group(ing).Need to prove,, for example can enumerate the monomer that vinylformic acid, methacrylic acid etc. have ethylenic linkage and functional group as monomer with functional group.
Particularly, can enumerate carboxylic styrene-butadiene copolymer, carboxylic styrene-isoprene multipolymer, carboxylic styrene butadiene saturated copolymer, carboxylic styrene-isoprene saturated copolymer, carboxylic styrene-ethylene-butylene-styrene multipolymer, carboxylic styrene-ethylene-butylene-styrene saturated copolymer, carboxylic acrylonitrile butadiene copolymer, amino modified polyol resin, amino modified phenoxy resin, amino modified acrylonitrile butadiene copolymer, polyvinyl butyral resin, polyvinyl acetal resin, carboxylic acrylonitrile butadiene copolymer, the acrylonitrile butadiene copolymer that contains the hydrogenation carboxyl, carboxylic acrylic rubber, the styrene-butadiene copolymer that contains maleic anhydride, the styrene-ethylene-butylene-styrene multipolymer that contains maleic anhydride, the saturated copolymer polyester resin of C-terminal, the saturated copolymer polyester resin of C-terminal, the styrenic block copolymer that contains epoxy group(ing), contain the styrene-ethylene-butylene copolymer of maleic anhydride etc.Need to prove " containing maleic anhydride " expression and maleic anhydride copolymerization.
Wherein, as commercially available product, can enumerate following products.
As carboxylic acrylonitrile butadiene copolymer, can enumerate Japanese ZEON society system trade(brand)name: Nipol 1072J, make trade(brand)name with society: Nipol DN631, emerging product society of space portion system trade(brand)name: Hycar CTBN, system trade(brand)name: the PNR-1H etc. of JSR society.
As containing amino acrylonitrile butadiene copolymer, can enumerate system trade(brand)name: the Hycar ATBN etc. of emerging product society of space portion.
As the styrene-ethylene-butadienecopolymer that contains maleic anhydride, can enumerate society of Asahi Chemical Industry system trade(brand)name: Tuftec M series product etc.
As the styrenic block copolymer that contains epoxy group(ing), can enumerate system trade(brand)name: the Epofriend etc. of DAICEL chemical industry society.
Wherein, in order to prevent that casting resin from leaking and not have glue residual, peelable, especially preferably contain the styrene-ethylene-butylene copolymer of maleic anhydride.In this multipolymer, maleic anhydride: vinylbenzene: the mass ratio of ethene-butylene (summation of ethene-butylene) is preferably 0.3～3: 10～40: 60～90, be preferably 0.5～1: 20～30: 70～80 especially.
With respect to binder layer 100 mass parts, reactive elastomeric usage quantity is preferably 30～95 mass parts, 40～90 mass parts more preferably.Usage quantity is 30 mass parts or 30 mass parts when above, can prevent further that flash or glue are residual.Usage quantity is 95 mass parts or 95 mass parts when following, can further improve separability, and more difficult generation glue is residual.
By making binder layer contain fluorine class additive, can further improve the peeling force of adhesive sheet.As fluorine class additive, can use the identical fluoride additive of fluorine class additive (c) that contains with above-mentioned first binder layer.
In addition, also can make curing catalysts such as comprising the solidifying agent elastomer crosslinked, dehydration catalyst in the binder layer with thermosetting resin, thermoplastic resin, fluoro-resin and reactivity.
Thermosetting resin and thermoplastic resin that above-mentioned thermosetting resin composition and thermoplastic resin can contain for the bonding coat that above-mentioned first self adhesive tape possesses.
In addition, in order to regulate thermal expansivity, thermal conductivity, surface viscosity, binding property etc., the bonding coat that the binder layer that the 3rd adhesive sheet possesses and first adhesive sheet possess similarly preferably adds inorganic or organic filler in binder layer.
The following describes the method that above-mentioned first～the 3rd binder layer is formed on a side surface of base material.Preferred following method: direct coating adhesive on base material, make it dry and form the casting method of binder layer, or with adhesive coated on releasable film, make its drying after, be transferred on the base material and form the lay-up method etc. of binder layer.
Need to prove that thermosetting resin composition and thermoplastic resin composition preferably together use with organic solvent.Aromatic series kind solvents such as toluene, dimethylbenzene, chlorobenzene for example; Ketones solvents such as acetone, methylethylketone, mibk; Non-proton class polar solvents such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone; Organic solvents such as tetrahydrofuran (THF).Above-mentioned organic solvent can be used alone, but also also mix together more than 2 kinds or 2 kinds.In the time of with an organic solvent, make preferably that 1 quality % in thermosetting resin and the thermoplastic resin composition or 1 quality % are above, preferred 5 quality % or the above dissolving of 5 quality %, make adhesive coated liquid and use.
When binder layer contains the thermosetting resin composition, preferably in adhesive coated liquid, cooperate solidifying agent such as 2-ethyl-4-methylimidazole, further cooperate curing catalyst as required.
Also can be formed on the structure of fitting strippable protective membrane, before the semiconductor device manufacturing, this protective membrane being peeled off on the binder layer of adhesive sheet of the present invention.In this case, from making adhesive sheet during use, can prevent that binder layer is impaired.As protective membrane; get final product so long as have the film of release property; can use any film, can list the film of formation such as polyester, polyethylene, polypropylene, polyethylene terephthalate and with silicone resin or fluorine cpd the demoulding is carried out on the surface of above-mentioned film and handled the film that forms etc.
In addition, the storage modulus after above-mentioned binder layer solidifies in 150 ℃～250 ℃ the temperature range be 0.1MPa or 0.1MPa above, be preferably 1MPa or 1MPa is above, 5MPa or more than the 5MPa more preferably.Need to prove, be meant the binder layer that in chip adhesive operation be in the state that be heated processing behind so-called the curing herein.In the wire-bonded operation that is used for making semiconductor device, in order to use bonding wire with semiconductor element and lead frame conducting, the two ends of this bonding wire are heated to 150～250 ℃, when carrying out clinkering with the ultrasonic wave of 60～120kHz, the binder layer that is arranged in the adhesive sheet under the lead frame is exposed to the above-mentioned high temperature that adds thermogenesis, by low elasticityization, absorb ultrasonic wave easily, lead frame vibration as a result, it is bad that wire-bonded takes place easily, but the adhesive sheet that has disposed the binder layer with above-mentioned storage modulus is difficult for taking place the problems referred to above.
(manufacture method of semiconductor device)
Based on Fig. 1 and Fig. 2, one of the method for using adhesive sheet of the present invention to make semiconductor device example is described.Be that example describes with the QFN that makes as semiconductor device below.
Need to prove that Fig. 1 is the lead frame plane sketch when the semiconductor element mounted thereon side is observed, to be expression make the process picture sheet of the method for QFN by lead frame shown in Figure 1 to Fig. 2 (a)～(f), the diagrammatic sectional view that lead frame is amplified along the A-A ' line of Fig. 1.
At first, prepare the lead frame 20 of brief configuration shown in Figure 1.Lead frame 20 possesses a plurality of island semiconductor element mounting portions (chip carrier portion) 21 of carrying semiconductor elements such as IC chip, along the circumferential arrangement a plurality of leads 22 of each semiconductor element equipped section 21.Secondly, shown in Fig. 2 (a), in the adhesive sheet bonding process, on a side surface of lead frame 20 (lower surface), the adhesive sheet 10 of the present invention of fitting makes binder layer (omitting among the figure) side become lead frame 20 sides.Need to prove, as the method that adhesive sheet 10 is fitted on the lead frame 20, preferred lay-up method etc.Next, shown in Fig. 2 (b), in the chip adhesive operation, use die attach adhesives (omitting among the figure) that never a fit side of adhesive sheet 10 of semiconductor elements 30 such as IC chip is carried in the mounting semiconductor element portion 21 of lead frame 20.
Then, in order to prevent under the effect of the thermal history that applies before the wire-bonded operation, evolving gas composition by generations such as adhesive sheet or die attach adhesives is attached to lead frame, reduce by the bad yield rate that causes of the joint of bonding wire, can be before the wire-bonded operation above-mentioned adhesive sheet, die attach adhesives, the lead frame that carried the IC chip be implemented the plasma carrying out washing treatment.
Next, shown in Fig. 2 (c), in the wire-bonded operation, by lead-in wire 22 electrically conductings of bonding wires such as gold thread 31 with semiconductor element 30 and lead frame 20.Then, shown in Fig. 2 (d), in the resin package operation, the semiconductor device in the manufacturing processed shown in Fig. 2 (c) is positioned in the model, use potting resin (molding material) to transmit mold (model forming), thereby with potting resin 40 packaging semiconductors 30.
Next, shown in Fig. 2 (e), in the adhesive sheet stripping process, adhesive sheet 10 is peeled off from potting resin 40 and lead frame 20, obtained being arranged with the QFN unit 60 of a plurality of QFN50.At last, shown in Fig. 2 (f), in cutting action, QFN unit 60 is cut open, made a plurality of QFN50 thus along the periphery of each QFN50.
(embodiment)
Next, illustrate in greater detail the present invention, but that the present invention does not limit is following with embodiment
Embodiment.
At first, the binder layer that obtains or the evaluation method of adhesive sheet are described.Estimate and carry out as described below.
The mensuration of＜storage modulus 〉
The joint compound solution coat that will make in each embodiment and comparative example is on releasable film, then, under drying conditions identical when making adhesive sheet, carry out drying, again (175 ℃ of the heat-treat conditions of chip adhesive operation, 2 hours) under heat-treat, make the releasable film have binder layer.
What should illustrate is to reach coating, the drying that 0.1mm carries out tackiness agent by dried thickness.The sample that obtains is cut into 5mm * 30mm.Using elastic modulus detection device (the system RHEOVIBRON DDV-II of Orientec society), is that 11Hz, heat-up rate are 3 ℃/minute, to measure temperature range be to measure under 150～250 ℃ the condition in frequency, and the result is as shown in the table.Need to prove that the numerical value in the following table provides the minimum value of measuring storage modulus in 150 ℃～250 ℃ of the temperature ranges.
The evaluation of＜adhesive sheet 〉
1. wire-bonded is bad
With lay-up method the adhesive sheet that obtains in each embodiment and the comparative example is fitted in QFN lead frame (the Cu lead frame of plating Au-Pd-Ni that outside dimension is 200mm * 60mm, 4 * 16 (counting 64) matrix sequences, size of components 10mm * 10mm, 84 pins) on.Then, use the epoxies die attach adhesives, with evaporation the illusory chip of aluminium (dummy chip) (6mm * 6mm, thickness 0.4mm) mounting semiconductor element portion of carrying lead frame.
Then, do not implement plasma and clean, and the use wire bonder (new Chuan She system, UTC-470BI), in Heating temperature is that 210 ℃, US POWER are 30, loading is that 0.59N, treatment time are under the condition of 10msec/ pin, uses gold thread that illusory chip and lead-in wire are conducted.64 semiconductor devices that inspection obtains detect as the bad generation number of wire-bonded with the semiconductor device number that lead-in wire side poor flow takes place.
Need to prove, in part embodiment and the comparative example, after being equipped on the mounting semiconductor element portion of lead frame, carrying out plasma and clean.The plasma cleaning condition is: and the use plasma etching apparatus (YAMATO science society system, trade(brand)name: V1000), using gas: Ar, gas flow: 45sccm, RF output rating: 450W, treatment time: 5 minutes.
2. flash
Lead frame after the bad evaluation of use wire-bonded carries out the flash evaluation.Utilizing epoxies mold agent (biphenyl epoxies, amount of filler 85 quality %), is that 180 ℃, pressure are 10MPa, treatment time to be under 3 minutes the condition in Heating temperature, by transmitting mold (model forming), with potting resin illusory chip is encapsulated.Check the semiconductor device after 64 resin package, potting resin is detected with the semiconductor device number of partly (the adhesive sheet side surface of lead-in wire) the generation number as flash attached to the outside conducting of lead-in wire.
3. glue is residual
Use the lead frame after flash is estimated, carry out the residual evaluation of glue.At first, be under the condition of 500mm/min at peeling rate, release adhesive thin slice from the lead frame.Check the semiconductor device after 64 adhesive sheets are peeled off, with adhesive attachment the outside conducting of lead-in wire with partly, the semiconductor device number that comprises on the adhesive sheet release surface of casting resin face detects as the residual generation number of glue.
4. bond strength
It is wide that the adhesive sheet that obtains in each embodiment and the comparative example is cut into 1cm, by the roller lamination be pressed together on 50mm * 100mm * 0.25mmt copper coin (METECS society of Mitsubishi system trade(brand)name: MF-202), and copper coin on the gold-plated plate.Then, after applying with chip adhesive and solidify (175 ℃ 1 hour), casting resin and solidifying (180 ℃ 4 hours) suitable thermal history, recover normal temperature.Above-mentioned plate is heated to 150 ℃, measures the stripping strength when the direction that becomes 90 ° with plate is peeled off the binder layer of the multilayer body that obtains.Make the Heating temperature of plate rise to 200 ℃, similarly measure stripping strength one time every 5 ℃ by 150 ℃.With the bond strength of 150～200 ℃ the minimum value of respectively measuring stripping strength under the temperature as adhesive sheet.
5. the evolving gas flow measurement of adhesive sheet
Using thermal mass to reduce determinator (SEIKO INSTRUMENTS society system, EZSTAR6000 series product, TG/DTA6300), is 10 ℃/minute at heat-up rate, to measure temperature be under 30～300 ℃ the condition, measures the rate of mass reduction of adhesive sheet.Rate of mass reduction is more little, and expression evolving gas amount is few more.
Embodiment 1～4 and comparative example 1～5
As shown in table 1 below, modulating adhesive is made adhesive sheet, and the binder layer or the adhesive sheet that obtain are estimated.
That is, in toluene, mix the preparation binder solution by composition and proportioning (mass parts) shown in the table 1.Then, as heat-resistant material, use polyimide resin film (Dong Li E.I.Du Pont Company system, trade(brand)name: Kapton 100EN, thickness is 25 μ m, second-order transition temperature is more than 300 ℃ or 300 ℃, and thermal expansivity is 16ppm/ ℃), be coated with above-mentioned binder solution thereon, making dried thickness is 6 μ m, then, under 120 ℃, make its dry 5 minutes, obtain having the adhesive sheet of binder layer.
Next, to the adhesive sheet that obtains carry out that above-mentioned wire-bonded is bad, flash, glue are residual, every evaluation of bond strength and evolving gas flow measurement.Evaluation result is shown in table 2 and table 3 (evolving gas flow measurement result).
Table 1-1
Embodiment
1 2 3 4
Thermosetting resin composition (a) Resins, epoxy *1 30 25 25
Resol *2 30 25 25
Vinyl fluoride vinyl ether co-polymer with functional group *9 30
Thermoplastic resin composition (b) Non-reacted elastomeric propylene nitrile-butadienecopolymer *3 40 40
Reactive elastomerics contains the styrene-ethylene-butylene copolymer of maleic anhydride *6 50 70
Fluorine class additive (c) Fluorine-containing class graftomer *4 1.5 0.5
Fluorinated block copolymer *7 0.5
Fluorine-containing aliphatic category polymer esters *8 1.5
Solidifying agent 2-ethyl-4-methylimidazole *5 0.5 0.5 0.5
*10 1
Table 1-2
Embodiment
1 2 3 4 5
Thermosetting resin composition (a) Resins, epoxy *1 45 35 35
Resol *2 25 35 35
Resins, epoxy *12 40
Resol *13 20
Thermoplastic resin composition (b) Non-reacted elastomeric propylene nitrile-butadienecopolymer *3 40 40
Reactive elastomerics contains the styrene-ethylene-butylene copolymer of maleic anhydride *6
Reactive elastomeric ring Styrene oxide 98min.-butadiene-styrene copolymer *11 30 30
Other Silicone oil *14 1.5 2
Silicon rubber *15 100
Silicon rubber *16 0.5
Solidifying agent 2-ethyl-4-methylimidazole *5 0.5 0.5 0.5 0.5
*1: big Japanese ink industry system trade(brand)name: the HP-7200 of society
*2: Japanese chemical drug system trade(brand)name: the TPM of society
*3: Japanese ZEON system trade(brand)name: the Nippol 1001 of society
*4: combine and grind chemical society system trade(brand)name: CHEMTREE LF-700 (solids component 7.5 quality %, solvent: the toluene methylethylketone)
*5: Tokyo changes into society's system
*6: society of Asahi Chemical Industry system trade(brand)name: Tuftec M-1911
*7: Japanese grease system trade(brand)name: the Modiper F200 (solids component 30 quality %, solvent methylethylketone mibk) of society
*8:3M society system trade(brand)name: Novec FC-4430
*9: Asahi Glass society system trade(brand)name: Lumiflon LF916
*10: Japanese polyurethane industry society system trade(brand)name: Colonate L
*11:DAICEL chemistry society system trade(brand)name: Epofriend AT501
*12: system trade(brand)name: the Epikote 1001 of japan epoxy resin society
*13: clear and system trade(brand)name: the CKM-2400 of polymer society
*14: system trade(brand)name: the KF-105 of chemical industry society of SHIN-ETSU HANTOTAI
*15: eastern Li Daokangningshe system, trade(brand)name: SD4580
*16: eastern Li Daokangningshe system, trade(brand)name: SRX212
Table 2
Wiring bad (individual) Flash (individual) Glue residual (individual) takes place Bond strength (N/cm)
Not gold-plated Gold-plated
Embodiment 1 0 0 0 1.05 0.82
2 0 0 0 0.86 0.74
3 0 0 0 1.30 1.07
4 0 0 0 0.68 0.62
Comparative example 1 2 0 63 5.43 4.36
2 1 0 59 6.01 5.71
3 17 0 0 1.26 1.00
4 13 4 0 0.99 0.80
5 20 32 41 0.64 0.67
Table 3
100 ℃ (quality %) 200 ℃ (quality %) 300 ℃ (quality %)
Embodiment 1 0.3 0.6 0.8
2 0.2 0.2 0.4
3 0.2 0.2 0.5
4 0.2 0.2 0.3
Comparative example 1 0.3 0.7 0.8
2 0.3 0.8 0.9
3 0.7 1.3 1.7
4 0.7 1.3 1.7
5 0.7 1.0 1.4
Embodiment 5,6 and 8
In toluene, mix the preparation binder solution by composition and proportioning (mass parts) shown in the table 4.Then, as heat-resistant material, use polyimide resin film (Dong Li E.I.Du Pont Company system, trade(brand)name: Kapton 100EN, thickness is 25 μ m, second-order transition temperature is more than 300 ℃ or 300 ℃, and thermal expansivity is 16ppm/ ℃), be coated with above-mentioned binder solution thereon, making dried thickness is 6 μ m, then, under 120 ℃, make its dry 5 minutes, obtain having the adhesive sheet of binder layer.
Embodiment 7,10 and 11
Change into by composition and proportioning shown in the table 4 and mixing in methylethylketone, in addition the preparation binder solution, obtains adhesive sheet of the present invention similarly to Example 5.
Embodiment 9
Prepare binder solution by composition and the proportioning identical with embodiment 5, next, as heat-resistant material, use 3/4 ounce Copper Foil (mining industry society of Mitsui Metal Co., Ltd. system trade(brand)name: 3EC-VLP, thickness 25 μ m, thermal expansivity 16ppm/ ℃), the above-mentioned binder solution of coating on its alligatoring face, making dried thickness is 8 μ m, 120 ℃ dry 5 minutes down, obtain having the adhesive sheet of the present embodiment of binder layer.
Comparative example 6 and 7
Change into by composition and proportioning shown in the table 4 and mixing in methylethylketone, in addition the preparation binder solution, is relatively used adhesive sheet similarly to Example 5.
Then, preparation has been implemented the adhesive sheet that plasma cleans to the adhesive sheet that obtains in embodiment 5～11, the comparative example 6 and 7 and has not been implemented 2 kinds of the thin slices that plasma cleans, and mensuration, the wire-bonded of carrying out above-mentioned storage modulus is bad, flash, glue is residual and every evaluation of bond strength.Measurement result is shown in table 5.
Table 4
Embodiment Comparative example
5 6 7 8 9 10 11 6 7
Thermosetting resin composition (a1) Fluoro-resin *17 5 20 10 15 5
Resins, epoxy A *18 10 10
Resins, epoxy B *19 5 5
Phenol-formaldehyde A *20 5 5
Bakelite B *21 5 5
Thermoplastic resin composition (b1) NBR *22 95 95 85
Ethylene-methyl acrylate-methyl propenoic acid glycidyl base ester copolymer resin *23 80 90
Acrylate-vinylformic acid glycidyl esters-acrylonitrile compolymer resin *24 90
SBR *25 85
Viton *26 85 90
Solidifying agent *27 1 1 1 1 1
Curing catalyst *28 1 1 1 1
(a1)/(b1) 0.05 0.25 0.11 0.17 0.05 0.17 0.11 0.17 0.11
*17: Asahi Glass society system, trade(brand)name: Lumiflon LF200F
*18: big Japanese ink chemical industry society system, trade(brand)name: HP-7200
*19: japan epoxy resin society system, trade(brand)name: Epikote 828
*20: clear and polymer society system, trade(brand)name: CKM2400
*21: Nippon Oil(Nippon Mitsubishi Oil) chemistry society system, trade(brand)name: DPP-6095H
*22: acrylonitrile butadiene copolymer resin, JSR society system, trade(brand)name: PNR-1H, quality molecular-weight average 330,000
*23: Sumitomo Chemical society system, trade(brand)name: Bondfast 7M, quality molecular-weight average 70,000
*24: Imperial Chemical Industries industry society system, SGP-3DR, quality molecular-weight average 1,000,000
*25: styrene butadiene copolymerization, society of Asahi Chemical Industry system, trade(brand)name: Tuftec M1911, quality molecular-weight average 110,000
*26: DOW society of Du Pont system, trade(brand)name: VITON VTR-7119, quality molecular-weight average 300,000
*27: Japanese polyurethane industry society system, trade(brand)name: Colonate L
*28: four countries change into society's system, 2-ethyl-4-methylimidazole (2E4MZ)
Table 5
Storage modulus (MPa) Wire-bonded bad (individual) Flash (individual) Glue residual (individual) takes place Bond strength (N/cm)
Plasma body does not have Plasma body has Plasma body does not have Plasma body has Plasma body does not have Plasma body has Plasma body does not have Plasma body has
Embodiment 5 5 0 0 0 0 0 0 2.35 1.96
6 1 0 0 0 0 0 0 1.47 1.57
7 0.5 0 0 0 0 0 0 0.98 0.78
8 3 0 0 0 0 0 0 2.65 2.06
9 5 0 0 0 0 0 0 2.35 1.96
10 0.5 0 0 0 0 0 0 0.49 0.39
11 0.2 0 0 0 0 0 0 0.59 0.44
Comparative example 6 6 22 0 7 0 0 25 5.88 5.10
7 2 31 0 8 8 0 29 6.86 5.98
As shown in table 5, adhesive sheet of the present invention does not take place fully that wire-bonded is bad, flash and glue is residual in having implemented the lead frame that plasma cleans.In contrast, the not fluorine-containing most generation of comparative example glue is residual.
Embodiment 12 and 13, comparative example 8 and 9
Form and proportioning (mass parts) shown in the according to the form below 6, embodiment 12, comparative example 8 and 9 are mixed to solids component in toluene be 20 quality %.Embodiment 13 is mixed to solids component in methylethylketone be 20 quality %, the preparation binder solution.
Then, use the binder solution obtain, similarly obtain having the adhesive sheet of binder layer, carry out the evaluation of adhesive sheet with the foregoing description 1～4.The results are shown in table 7.
Need to prove that the residual evaluation of flash in the table 7 and glue is carried out as described below.
Flash
Utilize lay-up method, it is that the QFN of 200mm * 60mm is with lead frame (plating the Cu lead frame of Au-Pd-Ni, 4 * 16 (adding up to 64) matrix sequences, size of components 10mm * 10mm, 84 pins) that the adhesive sheet that obtains in embodiment 12,13, the comparative example 8 and 9 is fitted in outside dimension.Then, in baking box, after carrying out being equivalent to the thermal treatment of chip adhesive in 1 hour under 175 ℃, carry out the plasma clean.The plasma cleaning condition for use plasma etching apparatus (YAMATO science society system, trade(brand)name: V1000), using gas: Ar, gas flow: 45sccm, RF output rating: 450W, treatment time: 5 minutes.Next, on hot plate, implement to be equivalent to the thermal treatment of wire-bonded under 220 ℃, 15 minutes the condition.Then, utilizing epoxies mold agent (the biphenyl epoxies contains filler 85 quality %), is that 180 ℃, pressure are 10MPa, treatment time to be under 3 minutes the condition in Heating temperature, by transmitting mold (model forming), carries out resin package.Check the semiconductor device after 64 resin package, potting resin is detected with the semiconductor device number of partly (the adhesive sheet side surface of lead-in wire) the generation number as flash attached to the outside conducting of lead-in wire.
Glue is residual
Use the lead frame after flash is estimated, carry out the residual evaluation of glue.At first, be under the condition of 500mm/min at peeling rate, release adhesive thin slice from the lead frame.Check the semiconductor device after 64 adhesive sheets are peeled off, will the outside conducting of lead-in wire with partly, comprise the semiconductor device number that is attached with tackiness agent on the adhesive sheet release surface of casting resin face and detect as the residual generation number of glue.
Table 6
Embodiment Comparative example
12 13 8 9
Fluoro-resin Vinyl fluoride vinyl ether co-polymer with functional group *29 30 10
Vinyl fluoride vinyl ether co-polymer with functional group *30 20
Reactive elastomerics Styrene-ethylene-the butylene copolymer that contains maleic anhydride *31 70
Carboxylic acrylonitrile butadiene copolymer *32 90
Carboxylic acrylonitrile butadiene copolymer *33 20
Other As non-reacted elastic body styrene-butadienecopolymer *34 80
As fluorine-free Syringaresinol urea formaldehyde *35 40
As fluorine-free resin Resins, epoxy *36 40
Solidifying agent *37 1 1 1
*38 8
*29: Asahi Glass society system trade(brand)name: Lumiflon LF916
*30: Asahi Glass society system trade(brand)name: Lumiflon LF200
*31: society of Asahi Chemical Industry system trade(brand)name: Tuftec M-1911 (styrene-ethylene-butylene copolymer, the maleic anhydride that contain maleic anhydride: vinylbenzene: the multipolymer of ethene-butylene (mass ratio)=0.5: 30: 70)
*System trade(brand)name: the PNR-1H of 32:JSR society
*33: Japanese ZEON society system trade(brand)name: Nipol 1072J
*34: society of Asahi Chemical Industry system trade(brand)name: Tuftec H-1041
*35: system trade(brand)name: the DPP-6095H of Nippon Oil(Nippon Mitsubishi Oil) chemistry society
*36: big Japanese ink chemical industry system trade(brand)name: the HP-7200 of society
*37: Japanese polyurethane industry society system trade(brand)name: Colonate L
*38: Tokyo changes into society's system (2-ethyl-4-methylimidazole)
Table 7
Flash (individual) Glue residual (individual) takes place
Embodiment 12 0 0
Embodiment 13 0 0
Comparative example 8 15 64
Comparative example 9 0 Can't peel off

Claims (16)

1. a semiconductor device adhesive sheet for producing is strippingly to be fitted in the lead frame of semiconductor device or the semiconductor device adhesive sheet for producing on the wiring substrate, it is characterized by
Possess base material and binder layer,
Described binder layer contains thermosetting resin composition (a), thermoplastic resin composition (b) and fluorine class additive (c).
2. semiconductor device adhesive sheet for producing as claimed in claim 1 is characterized by, and described fluorine class additive (c) is for being selected from more than a kind or a kind of fluorine-containing graftomer, fluorinated block copolymer and fluorine-containing aliphatic category polymer esters.
3. a semiconductor device adhesive sheet for producing is strippingly to be fitted in the lead frame of semiconductor device or the semiconductor device adhesive sheet for producing on the wiring substrate, it is characterized by,
Possess base material and binder layer,
Described binder layer contains fluoro-resin.
4. semiconductor device adhesive sheet for producing as claimed in claim 3, it is characterized by, described binder layer contains thermosetting resin composition (a1) and thermoplastic resin composition (b1), and any in this thermosetting resin composition (a1) and the thermoplastic resin composition (b1) is the olefine kind resin that contains fluorine.
5. semiconductor device adhesive sheet for producing as claimed in claim 4 is characterized by, and the thermosetting resin composition (a1) of described binder layer and the mass ratio (a1)/(b1) of thermoplastic resin composition (b1) are 0.05～0.43.
6. semiconductor device adhesive sheet for producing as claimed in claim 4 is characterized by, and the quality molecular-weight average of thermoplastic resin composition (b1) is 2,000～1,000,000.
7. semiconductor device adhesive sheet for producing as claimed in claim 3 is characterized by, and the storage modulus after described binder layer solidifies is 0.1MPa or more than the 0.1MPa in the time of 150～250 ℃.
8. as claim 1 or 3 described semiconductor device adhesive sheet for producing, it is characterized by, the bond strength in the time of 150～200 ℃ of the described binder layer after the curing is 0.03～5N/cm.
9. as claim 1 or 3 described semiconductor device adhesive sheet for producing, it is characterized by, described base material is that second-order transition temperature is more than 150 ℃ or 150 ℃, thermal expansivity is 5～50ppm/ ℃ thermotolerance film.
10. as claim 1 or 3 described semiconductor device adhesive sheet for producing, it is characterized by, described base material is that thermal expansivity is 5～50ppm/ ℃ a tinsel.
11. a semiconductor device adhesive sheet for producing is strippingly to be fitted in the lead frame of semiconductor device or the semiconductor device adhesive sheet for producing on the wiring substrate, it is characterized by,
Possess base material and binder layer,
Described binder layer contains fluoro-resin and reactive elastomerics.
12. semiconductor device adhesive sheet for producing as claimed in claim 11, it is characterized by, described fluoro-resin is to contain the multipolymer that the raw material monomer of fluoroolefin and vinyl ether is polymerized and/or contain fluoroolefin and multipolymer that the raw material monomer of vinyl ester is polymerized.
13. semiconductor device adhesive sheet for producing as claimed in claim 11 is characterized by, described reactive elastomerics is the styrene-ethylene-butylene copolymer that contains maleic anhydride.
14. each the described semiconductor device adhesive sheet for producing as in the claim 1,3 and 11 is characterized by, and on the single face of binder layer protective membrane is set.
15. a semiconductor device is characterized by, this semiconductor device is to use the semiconductor device adhesive sheet for producing of each record in the claim 1,3 and 11 to make.
16. the manufacture method of a semiconductor device is characterized by, this manufacture method uses the semiconductor device adhesive sheet for producing of each record in the claim 1,3 and 11 to make.
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CN100500784C (en) 2009-06-17
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CN101445707A (en) 2009-06-03
JP4654062B2 (en) 2011-03-16

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