CN102190973A - Film for manufacturing semiconductor device and method of manufacturing semiconductor device - Google Patents

Film for manufacturing semiconductor device and method of manufacturing semiconductor device Download PDF

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Publication number
CN102190973A
CN102190973A CN2011100362808A CN201110036280A CN102190973A CN 102190973 A CN102190973 A CN 102190973A CN 2011100362808 A CN2011100362808 A CN 2011100362808A CN 201110036280 A CN201110036280 A CN 201110036280A CN 102190973 A CN102190973 A CN 102190973A
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CN
China
Prior art keywords
binder layer
layer
semiconductor device
film
adhesive layer
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CN2011100362808A
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Chinese (zh)
Inventor
菅生悠树
田中俊平
松村健
井上泰史
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of CN102190973A publication Critical patent/CN102190973A/en
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • 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
    • 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
    • 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
    • H01L24/80—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
    • H01L24/83—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
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01029—Copper [Cu]
    • 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

Abstract

There is provided a new film for manufacturing a semiconductor device that is superior to prevent contamination of a semiconductor chip having an excellent balance of holding power during dicing a semiconductor wafer even where the semiconductor wafer is thin, peeling property when peeling the semiconductor chip that is obtained by dicing together with its adhesive layer, and low contamination property in which there is no attachment of cutting debris to the semiconductor chip. A film for manufacturing a semiconductor device that is used when manufacturing a semiconductor device has a base layer, a first pressure-sensitive adhesive layer that is provided on the base layer, a radiation curing-type second pressure-sensitive adhesive layer that is provided on the first pressure-sensitive adhesive layer and cured by radiation irradiation in advance, and an adhesive layer that is provided on the second pressure-sensitive adhesive layer.

Description

Semiconductor device is made the manufacture method with film and semiconductor device
Technical field
The present invention relates to the semiconductor device manufacturing film that uses in the manufacturing of semiconductor device, more specifically, relate to semiconductor wafer cutting and after forming semi-conductor chip the semiconductor device manufacturing film of use in gluing series of processes till being fixed on the adherend etc. with this semi-conductor chip.In addition, the present invention relates to use the method for described semiconductor device manufacturing with the thin film fabrication semiconductor device.
Background technology
Be formed with the semiconductor wafer of circuit pattern, by behind the grinding back surface adjusting thickness, be cut into semi-conductor chip (cutting action) as required.In cutting action, in order to remove incised layer, generally the hydraulic pressure with appropriateness (is generally about 2kg/cm 2) the cleaning semiconductor wafer.Then, utilize tackiness agent described semi-conductor chip to be joined on the adherends such as lead frame.In this operation, tackiness agent is applied on lead frame or the semi-conductor chip.But, being difficult to realize the homogenizing of adhesive layer by this method, the coating of tackiness agent needs special device or needs long-time in addition.Therefore, the dicing/die bonding film (for example, with reference to Japanese kokai publication sho 60-57642 communique) that also provides the required chip set of chip join to stick with glue the agent layer in the gluing maintenance semiconductor wafer has been proposed in cutting action.
In the dicing/die bonding film of record, support film (substrate layer) is provided with binding property peel ply (binder layer) and electrically conductive adhesive layer in patent documentation 1.That is, behind cutting semiconductor chip under the maintenance of adhesive layer, support film is stretched and semi-conductor chip and adhesive layer are together peeled off, each reclaims with it, is affixed to via this adhesive layer then on the adherend such as lead frame.
The adhesive layer of this dicing/die bonding film, can not to cut or scale error etc. in order not producing, to wish to have the good confining force of semiconductor wafer and the good separability that the semi-conductor chip after the cutting and adhesive layer can be peeled off from support base material integratedly.In addition, the binder layer of wishing dicing/die bonding film has, and the good confining force of lead frame, disperse and adaptation tackiness agent of the semi-conductor chip of panelization and when cutting produce when being used to prevent to cut cutting swarf are not adhered to low contaminative on the semi-conductor chip that has adhesive layer.
But, want to bring into play these characteristics and be not easy with good balance, particularly in recent years, semi-conductor chip is that purpose is carried out slimming and big area development with the high capacity, therefore makes substrate layer and binder layer satisfy the various requirement difficulty more that becomes.That is, because therefore existing dicing/die bonding film can not bring into play described characteristic with good balance not respectively by the characteristic of the corresponding various requirement of function.
Therefore, in order to address these problems, various modification methods have been proposed.For example, in patent documentation 2, disclose that cutting blade, stripping film, chip adhered film and mould release film stack gradually and the cutting self adhesive tape that obtains.This cutting is with in the self adhesive tape, on cutting blade, reset stripping film, and make the peeling force of the peeling force of stripping film and chip adhered film less than stripping film and cutting blade, when the picking up of semi-conductor chip, can easily chip adhered film and semi-conductor chip together be peeled off thus.In addition, paste formation on the cutting blade owing to have cutting frame (cut ring), so the fixed function of cut ring is guaranteed.Promptly, the cutting self adhesive tape of record in the patent documentation 2, by between cutting blade and chip adhered film, stripping film being set, and the performance of the dicing/die bonding film of all the time being sought, the separability such different function separated structures of the tackiness when being about to have when picking up with cutting.
But, even the cutting self adhesive tape of record in the patent documentation 2, when the cutting of semiconductor wafer, also produce cutting swarf from cutting blade, this cutting swarf is attached to the side of semi-conductor chip etc. with burr (バ リ) or form that carefully must (ヒ ゲ), the problem that exists the fabrication yield of semiconductor device to descend thus.
Patent documentation 1: Japanese kokai publication sho 60-57642 communique
Patent documentation 2: TOHKEMY 2006-203000 communique
Summary of the invention
The present invention makes in order to solve described problem, even it is under the slim situation that its purpose is to provide semiconductor wafer, the novel semi-conductor device that the equilibrium response contamination preventing good, semi-conductor chip of the low contaminative of non-cohesive cutting swarf is good on separability the when confining force when cutting this thin semiconductor wafer, the semi-conductor chip that will obtain by cutting and its adhesive layer are peeled off integratedly and the described semi-conductor chip is made the manufacture method with film and semiconductor device.
The applicant etc. study with the manufacture method of film and semiconductor device the semiconductor device manufacturing in order to address the above problem.Found that, by adopting following formation, can realize above-mentioned purpose, thereby finish the present invention.
Semi-conductor manufacturing film of the present invention, in order to solve above-mentioned problem, be the semi-conductor manufacturing film that uses when semi-conductive make, it is characterized in that, comprise: substrate layer, be arranged on first binder layer on the described substrate layer, be arranged on described first binder layer and second binder layer by illumination radiation line and solidified radiation curing type and be arranged on adhesive layer on described second binder layer in advance.
The existing dicing/die bonding film that uses in the manufacturing of semiconductor device generally has the structure that stacks gradually binder layer and adhesive layer on substrate layer.And, the separability that described binder layer requires to have binding property that the chip that can prevent semi-conductor chip when the cutting of semiconductor wafer disperses and can be easily when the picking up of described semi-conductor chip peels off with adhesive layer.That is, binder layer requires opposite performance at cutting action with picking up in the operation.
On the other hand, among the present invention, according to said structure, by set gradually first binder layer and second binder layer on substrate layer, the function of the separability of the binding property in the time of can realizing the desired cutting of the binder layer of existing dicing/die bonding film when picking up is separated.That is, first binder layer is gluing fixing with second binder layer, when therefore the semiconductor wafer of pasting on the adhesive layer being cut, can prevent that the chip of semi-conductor chip from dispersing.Do not require separability when picking up for first binder layer, therefore the substrate layer structure that is provided with first binder layer plays the function as a kind of carrier band.On the other hand, second binder layer solidifies in advance by the illumination radiation line, therefore adhesive layer is shown good separability.Therefore, can carry out picking up of semi-conductor chip well.In addition, also the operation of picking up the front irradiation radiation can be omitted.
In addition, in the existing dicing/die bonding film, during the cutting of semiconductor wafer, the penetraction depth of cutting blade etc. is arrived binder layer or substrate layer.But, when cutting proceeds to binder layer a part of, thus sometimes on cut surface the part of binder layer become burr or carefully must be attached to the border of binder layer and adhesive layer.In addition, when cutting proceeds to substrate layer, produce thread cutting swarf sometimes, pollute semi-conductor chip.But among the present invention, owing to be the structure that is laminated with first binder layer and second binder layer on substrate layer, so the penetraction depth of cutting blade etc. needn't proceed to first binder layer, can stop at second binder layer.In addition, second binder layer solidifies in advance by the illumination radiation line, thereby the part that therefore can be suppressed at second binder layer on the cut surface becomes the border that burr is attached to second binder layer and adhesive layer.As a result, can pick up the semi-conductor chip that has adhesive layer well.In addition, cutting needn't proceed to substrate layer, does not therefore also produce thread cutting swarf.Therefore, semiconductor device manufacturing film of the present invention can be realized the low contaminative to semi-conductor chip.
In the described formation, preferably: described second binder layer and adhesive layer are provided with in the mode of the inboard that drops into the cut ring adhesive portion in described first binder layer at least, the planeform of described adhesive layer is bigger than described second binder layer, and described adhesive layer is provided with in the mode that covers whole second binder layer, in addition, be not positioned at the periphery on described second binder layer in the described adhesive layer, be arranged on described first binder layer.
According to described formation,, therefore when cutting, can fix this cut ring reliably owing to can on first binder layer that does not require the separability when picking up, paste cut ring.In addition, compare, when the cut ring after using is peeled off, also can suppress the generation that adhesive paste adheres to the situation of on adhesive layer, pasting cut ring.In addition, the planeform of adhesive layer is greater than second binder layer, and is provided with in the mode that covers whole second binder layer.In addition, the periphery of adhesive layer is not arranged on second binder layer and is arranged on first binder layer, is firm gluing formation, and tackiness agent is peeled off and produced and crispatura from second binder layer in the time of therefore for example can preventing to cut.
In the described formation, preferred: described substrate layer, described first binder layer and described second binder layer are piled up the works (for example cutting film) that forms, and the flexural rigidity S that is calculated by E * I is 5.0 * 10 4～7.0 * 10 5Scope in.(wherein, I is with b * T 3The cross section second moments of/12 expressions, b is the width 10 (mm) of the test film of described works, T is the thickness (mm) of described works, E is the stretching energy storage Young's modulus (Pa) under 25 ℃ of described works).By described flexural rigidity S is set at 5.0 * 10 4More than, can keep the rigidity of described works, when pasting, can under the situation that does not produce fold, paste wafer.On the other hand, by described flexural rigidity S is set at 7.0 * 10 5Below, described works is suitably crooked when picking up, and can realize stable picking up.
In the described formation, the stripping strength X between preferred described second binder layer and the adhesive layer is in the scope of 0.01N/20mm～0.2N/20mm.By the stripping strength X between second binder layer and the adhesive layer is set at more than the 0.01N/20mm, for example, when the cutting of semiconductor wafer, can prevents to produce between the two and peel off and prevent that semi-conductor chip from producing chip and dispersing.On the other hand, by described stripping strength X is set at below the 0.2N/20mm, even omit the irradiation process of radiation, also picking up semiconductor chip well.
In the described formation, the stripping strength Y between preferred described first binder layer and second binder layer is in the scope of 0.2N/20mm～10N/20mm.By the stripping strength Y between first binder layer and second binder layer is set at more than the 0.2N/20mm, for example, can be reliably during cutting fixedly semiconductor wafer or semi-conductor chip.In addition,, second binder layer can be peeled off from first binder layer, the laminate film as the carrier band that is made of the substrate layer and first binder layer can be utilized again by described stripping strength Y is set at below the 10N/20mm.
In the described formation, stripping strength X between preferred described second binder layer and the adhesive layer and the ratio (Y/X) of the stripping strength Y between described first binder layer and second binder layer are in 3～500 scope.By described stripping strength X is set at more than 3 with the ratio (Y/X) of stripping strength Y, peel off the border that the interface is positioned at second binder layer and adhesive layer in the time of can making the picking up of semi-conductor chip.On the other hand by being set at below 500 than (Y/X) described, the chip in the time of can suppressing to cut disperses or the crispaturaing of adhesive layer, and can stably cut.
In the described formation, the thickness of preferred described second binder layer is in the scope of 10 μ m～100 μ m.By the thickness setting with second binder layer is that the penetraction depth of cutting blade reaches first binder layer in the time of can preventing to cut more than the 10 μ m.On the other hand, be below the 100 μ m by thickness setting with second binder layer, can carry out the stable of semi-conductor chip and pick up.
In the described formation, the stripping strength between preferred described first binder layer and the SUS304-BA plate is in the scope of 0.2N/20mm～11N/20mm.By the stripping strength between first binder layer and the SUS304-BA plate is set at more than the 0.2N/20mm, can cut ring is gluing reliably fixing, thus can pick up well.On the other hand, by described stripping strength is set at below the 11N/20mm, when the cut ring after will using is peeled off from first binder layer, can reduce on cut ring, producing the residual phenomenon of adhesive paste.
In the described formation, preferred described second binder layer is by being formed on the binder layer on described first binder layer after the precursor cures of illumination radiation line with this second binder layer.
In the described formation, preferred described second binder layer is to be arranged on described first binder layer by the precursor with this second binder layer to be cured the binder layer that forms by the illumination radiation line afterwards.
In the described formation, preferred described adhesive layer is the adhesive layer that forms on solidified second binder layer by the illumination radiation line in advance.
In the described formation, preferred described adhesive layer is arranged on by the illumination radiation line and is cured on the precursor of second binder layer before.
In the described formation, preferred described adhesive layer is formed by Resins, epoxy, phenol resins and acrylic resin at least.
In the described formation, the second-order transition temperature of preferred described acrylic resin is in-30 ℃～10 ℃ scope.Be set at more than-30 ℃ the energy storage Young's modulus of (for example, 100 ℃～200 ℃) in the time of can keeping the high temperature of adhesive layer by second-order transition temperature with acrylic resin.On the other hand, by described second-order transition temperature is set at below 10 ℃, can realize good adaptation, adhibit quality to semiconductor wafer.
In the described formation, preferred described second binder layer is formed by acrylic polymers at least.
The manufacture method of semiconductor device of the present invention, in order to solve described problem, use the method for thin film fabrication semiconductor device for the semiconductor device manufacturing of using described middle record, it is characterized in that, described method comprises following operation at least: in the operation of described semiconductor device manufacturing with crimping semiconductor wafer on the described adhesive layer of film, thereby described semiconductor wafer is cut the operation that forms semi-conductor chip with described adhesive layer, wherein, the penetraction depth of cutting stops at described second binder layer, with the operation that described semi-conductor chip is peeled off from described second binder layer with described adhesive layer, and, stripping process from the crimping process of described semiconductor wafer to semi-conductor chip is not to the described second binder layer illumination radiation line.
In the described method, use the semiconductor device manufacturing of the structure that on substrate layer, stacks gradually first binder layer, second binder layer and adhesive layer to carry out the manufacturing of semiconductor device with film.At this, described first binder layer is gluing fixing with second binder layer, therefore when the cutting of semiconductor wafer, can prevent that the chip of semi-conductor chip from dispersing.In addition, in the cutting of semiconductor wafer because the penetraction depth of cutting blade stops at second binder layer, therefore can prevent the cutting swarf that when the cutting substrate layer, produces become burr or carefully must and be attached on the semi-conductor chip.In addition, second binder layer solidifies by illumination radiation line in advance, the part that therefore can be suppressed at second binder layer on the cut surface become burr or carefully must and be attached to the border of second binder layer and adhesive layer.As a result, can pick up the semi-conductor chip that has adhesive layer well.
In addition, second binder layer solidifies in advance by the illumination radiation line, therefore adhesive layer is shown good separability.Therefore, can carry out picking up of semi-conductor chip well.In addition, at stripping process, needn't therefore can reduce process number to the described second binder layer illumination radiation line from the crimping process of semiconductor wafer to semi-conductor chip.
The invention effect
By the means of explanation in described, the present invention realizes following effect.Promptly, according to semiconductor device manufacturing film of the present invention, by adopting the structure that on substrate layer, sets gradually first binder layer, second binder layer and adhesive layer, first binder layer is given the gluing reliably fixed function of second binder layer, and by to second binder layer in advance the illumination radiation line it is solidified, thereby given the good separability with adhesive layer.That is, will be desired to the binder layer of existing dicing/die bonding film, the separability of the binding property during cutting when picking up carried out function and separated.As a result, even semi-conductor chip is under the situation of slimming, maximization, the semiconductor device manufacturing film that the separability when confining force in the time of also can obtaining cutting semiconductor chip and picking up semiconductor chip is good.In addition, during cutting, can not will penetraction depth proceed to substrate layer, but stop at second binder layer, therefore can suppress the generation of cutting swarf, can reduce this cutting swarf and be attached on the semi-conductor chip.That is,, can provide the low good semiconductor device manufacturing film of contaminative according to the present invention.In addition,, carry out the manufacturing of semiconductor device with film, can improve yield rate by using described semiconductor device manufacturing according to the manufacture method of semiconductor device of the present invention.
Description of drawings
Fig. 1 is the diagrammatic cross-section of the semiconductor device manufacturing of expression an embodiment of the invention with film.
Fig. 2 is the vertical view when partition one side is watched described semiconductor device manufacturing with film.
Fig. 3 is to use the explanatory view of described semiconductor device manufacturing with the manufacture method of the semiconductor device of film, Fig. 3 (a) is illustrated in the operation of semiconductor device manufacturing with stickup semiconductor wafer on the film, the operation of the described semiconductor wafer of Fig. 3 (b) expression cutting, the operation of Fig. 3 (c) expression picking up semiconductor chip.
Label declaration
1 semiconductor device manufacturing film
11 substrate layers
12 first binder layers
13 second binder layers
14 adhesive layers
The 14a periphery
15 partitions
The adhesive portion of 18 cut ring
21 semiconductor wafers
22 semi-conductor chips
23 cut ring
24 cutting blades
Embodiment
(semiconductor device manufacturing film)
Below with reference to Fig. 1 and Fig. 2 the semiconductor device manufacturing of embodiments of the present invention is described with film.Fig. 1 is the diagrammatic cross-section of the semiconductor device manufacturing of expression an embodiment of the invention with film.Fig. 2 is the vertical view when partition one side is watched described semiconductor device manufacturing with film.
As shown in Figure 1, the semiconductor device manufacturing has the formation that is disposed with first binder layer 12, second binder layer 13 and adhesive layer 14 on substrate layer 11 at least with film 10.In addition, semiconductor device manufacturing of the present invention is with film 11, as shown in Figure 1, can be provided with the partition 15 on the surface that is used to protect first binder layer 12 and adhesive layer 14.In addition, the described substrate layer 11 and first binder layer 12 are used for second binder layer 13 and cut ring described later gluing fixing, play the effect as carrier band.
[substrate layer]
The constituent material of described substrate layer 11 is not particularly limited, and for example can enumerate: by new LDPE (film grade), linear polyethylene, medium-density polyethylene, high density polyethylene(HDPE), ultra-low density polyethylene, atactic copolymerized polypropene, block copolymerization polypropylene, homo-polypropylene, polybutene, polyolefine such as polymethylpentene, vinyl-vinyl acetate copolymer, ethylene-propylene copolymer, ionomer resin, ethene-(methyl) acrylic copolymer, ethene-(methyl) acrylate is (random, alternately) multipolymer, ethylene-butene copolymer, ethene-hexene copolymer, urethane, polyethylene terephthalate, polyester such as PEN, polycarbonate, polyimide, polyether-ether-ketone, polyimide, polyetherimide, polymeric amide, fully aromatic polyamide, polyphenylene sulfide, aromatic poly (paper), glass, woven fiber glass, fluorine resin, polyvinyl chloride, polyvinylidene dichloride, cellulosic resin, polyorganosiloxane resin, the plastics film that their mixture etc. constitute.In addition, as the material of substrate layer 11, can enumerate the polymkeric substance such as cross-linking agent of described resin.Described plastics film can not stretch and uses, and can carry out as required using after single shaft or the biaxial stretch-formed processing yet.
In order to improve and the adaptation of first binder layer 12 and retentivity etc., the surface treatment that the surface of described substrate layer 11 can be habitually practised.As this method, for example can enumerate: chemistry such as chromic acid processing, ozone exposure, fire exposure, high-voltage electric shock exposure, ionizing ray processing or physical treatment, silane coupling agent (for example, adhesive substance described later) coating are handled.
The constituent material of described substrate layer 11 can suitably select of the same race or foreign material uses.In addition, also multiple material mixing can be used as required.In addition, in order to give antistatic effect, substrate layer 11 also can use described plastics film to be provided with to be formed by metal, alloy or their oxide compound etc., thickness is the film of evaporation layer of the conducting material of about 30 dusts～about 500 dusts.In addition, also can use between the described film or the layered product that obtains with other film applying etc.In addition, substrate layer 11 individual layer or will the two-layer above film that uses described material etc. carry out the multiple stratification more than two-layer and the laminate film that obtains.
The thickness of substrate layer 11 so long as the degree that does not rupture when expansion described later then is not particularly limited, can suitably be set.General preferred in the scope of about 5 μ m～about 200 μ m.
[first binder layer]
First binder layer 12 is arranged on the substrate layer 11, is to be used for second binder layer 13 and the gluing fixed layer of cut ring.Among Fig. 1, first binder layer 12 is arranged on the whole orthogonal substrate layer 11, and planeform is a rectangle, still, also can be circular.In addition, during the picking up of semi-conductor chip described later, between second binder layer 13 and adhesive layer 14, peel off the stripping performance when therefore special requirement are not picked up for first binder layer 12.That is, the fundamental property of first binder layer 12 is binding propertys.Therefore, the constituent material of first binder layer 12 is not particularly limited, and can adopt existing material known.
As the tackiness agent that constitutes first binder layer 12, can use the pressure sensitive adhesive of general use.Particularly, for example can enumerate: various tackiness agents such as acrylic adhesives, rubber adhesive, polysiloxane-based tackiness agent, polyvinyl ether tackiness agent.Wherein, consider from the viewpoints such as cleaning of utilizing organic solvents such as ultrapure water or alcohol to clean, preferably with (methyl) acrylic polymers (methyl) acrylic adhesives as base polymer for the semiconductor wafer as the tackiness of the semiconductor wafer of material to be cut or semiconductor packages, after peeling off etc.In addition, so-called (methyl) for example under the situation of (methyl) acrylic polymers, is meant acrylic polymers and methacrylic polymer both sides.At this moment, illustrative compound below too.
As described (methyl) acrylic polymers, (for example for example can enumerate (methyl) alkyl acrylate, 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, the 2-ethylhexyl, different monooctyl ester, different ninth of the ten Heavenly Stems ester, the last of the ten Heavenly stems ester, the isodecyl ester, the undecane ester, the dodecane ester, the tridecane ester, tetradecane ester, the n-Hexadecane ester, the octadecane ester, the alkyl of carbonatomss 1～30 such as eicosane ester, straight or branched alkyl ester of carbonatoms 4～18 etc. particularly), (methyl) vinylformic acid cycloalkanes ester (for example, the ring pentyl ester, cyclohexyl etc.), (methyl) hydroxyalkyl acrylate (for example, the hydroxyl ethyl ester, hydroxy butyl ester, the own ester of hydroxyl etc.), (methyl) glycidyl acrylate, (methyl) vinylformic acid, methylene-succinic acid, maleic anhydride, (methyl) acrylamide, N-methylol (methyl) acrylamide, (methyl) alkyl acrylate aminoalkyl ester (for example, dimethylaminoethyl methacrylate, methacrylic acid uncle fourth amino ethyl ester etc.), vinyl-acetic ester, cinnamic one or more as (methyl) acrylic polymers of monomer component etc.
Described (methyl) acrylic polymers, in order to improve cohesive force and tackiness etc., also can contain as required with can with the corresponding unit of other monomer component of described (methyl) alkyl acrylate or the copolymerization of cycloalkanes ester.As such monomer component, for example can enumerate: vinylformic acid, methacrylic acid, (methyl) vinylformic acid carboxylic ethyl ester, (methyl) vinylformic acid carboxylic pentyl ester, methylene-succinic acid, toxilic acid, fumaric acid, Ba Dousuan etc. contain carboxylic monomer; Anhydride monomers such as maleic anhydride, itaconic anhydride; Hydroxyl monomers such as (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-2-hydroxy propyl ester, (methyl) vinylformic acid-4-hydroxyl butyl ester, (methyl) vinylformic acid-own ester of 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-hydroxyl dodecane ester, (methyl) vinylformic acid (4-methylol cyclohexyl) methyl esters; Styrene sulfonic acid, allyl sulfonic acid, 2-(methyl) acrylamido-2-methyl propane sulfonic acid, (methyl) acrylamido propanesulfonic acid, (methyl) vinylformic acid sulphur propyl ester, (methyl) acryloxy naphthene sulfonic acid etc. contain the sulfonic group monomer; Acryloyl phosphoric acid-phosphorous acidic group monomers such as 2-hydroxy methacrylate; Acrylamide, vinyl cyanide etc.These copolymerisable monomer compositions can use one or more.The usage quantity of these copolymerisable monomers is preferably below the 30 weight % of whole monomer components, further below the preferred 15 weight %.
In addition, crosslinked in order to carry out, described (methyl) acrylic polymers also can contain polyfunctional monomer etc. as required as the comonomer composition.By base polymer is crosslinked, therefore the self-supporting property improvement of binder layer can prevent the remarkable distortion of adhesive sheet, keeps the dull and stereotyped state of first binder layer 12 easily.
As polyfunctional monomer, for example can enumerate: 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 be can use a kind of or two or more.The usage quantity of polyfunctional monomer is considered to be preferably below the 30 weight % of whole monomer components from viewpoints such as adhesion characteristics.
Described (methyl) acrylic polymers can be by obtaining single monomer or two or more monomeric polymerization of mixtures.Polymerization can be undertaken by the any-mode of solution polymerization, letex polymerization, mass polymerization, suspension polymerization, photopolymerization etc.Particularly under the situation of irradiation ultraviolet radiation or electron rays israds, preferably carry out curtain coating and carry out photopolymerization and synthesize (methyl) acrylic polymers by the liquid composition that will in carbamate (methyl) acrylate quasi-oligomer, cooperate monomer component and Photoepolymerizationinitiater initiater to obtain.
Described carbamate (methyl) acrylate quasi-oligomer, be number-average molecular weight be about 500～about 100,000, preferred 1000～30,000, and be the difunctional compound of main framing with the esterdiol.In addition, as monomer component, can enumerate morpholine (methyl) acrylate, (methyl) isobornyl acrylate, dicyclo pentyl (methyl) acrylate (ジ シ Network ロ ペ Application タ ニ Le (メ タ) ア Network リ レ one ト), double cyclopentenyl (methyl) acrylate (ジ シ Network ロ ペ Application テ ニ Le (メ タ) ア Network リ レ one ト), methoxylation ring triolefin in the last of the ten Heavenly stems (methyl) acrylate etc.The ratio of mixture of carbamate (methyl) acrylate quasi-oligomer and monomer component, preferred oligopolymer: monomer component=95～5: 5～95 (weight %), more preferably 50～70: 50～30 (weight %).When the content of carbamate (methyl) acrylate quasi-oligomer was high, the viscosity of liquid composition uprised, and therefore had the polymeric of being difficult to tendency.
Consider that from the viewpoint of cohesive force that the weight-average molecular weight of described (methyl) acrylic polymers is preferably is about 100,000～about 1,000,000, more preferably from about 150,000～about 900,000.
In addition, in order to improve the number-average molecular weight of (methyl) acrylic polymers as base polymer etc., also can suitably use outside linking agent in the described tackiness agent.As the concrete means of outside cross-linking method, can enumerate: add the method that so-called linking agents such as polyisocyanate compound, melamine-type resins, urea resin, Resins, epoxy, polyamines, carbonyl bearing polymer react.Use under the situation of outside linking agent, its usage quantity is according to carrying out suitably determining with the balance of the crosslinked base polymer of desire and as the use of tackiness agent.Generally preferably cooperate about 1 weight part～about 5 weight parts with respect to described base polymer 100 weight parts.In addition, except that described composition, can also use additives such as existing known various tackifier, antiaging agent in the tackiness agent as required.
The thickness of first binder layer 12 is not particularly limited, considers from fusible viewpoint, and preferably in the scope of 1 μ m～30 μ m, the more preferably scope of 2 μ m～25 μ m, the scope of preferred especially 3 μ m～20 μ m.
Stripping strength between first binder layer 12 and the cut ring is preferably in the scope of 0.2N/20mm～10N/20mm, more preferably in the scope of 0.3N/20mm～9.5N/20mm, in the scope particularly preferably in 0.5N/20mm～9N/20mm.By the stripping strength between first binder layer 12 and the cut ring is set at more than the 0.2N/20mm, can this cut ring is gluing reliably fixing, cut well.On the other hand, by described stripping strength is set at below the 10N/20mm, the cut ring after can will using when suppressing the residual generation of adhesive paste is peeled off from first binder layer.
In addition, in the scope of not damaging effect of the present invention etc., also can contain various additives (for example, tinting material, thickening material, extender, weighting agent, tackifier, softening agent, antiaging agent, antioxidant, tensio-active agent, linking agent etc.) in first binder layer 12.
[second binder layer]
Second binder layer 13 is arranged on first binder layer 12.Second binder layer 13 plays the function that the penetraction depth that prevents cutting blade etc. when cutting semiconductor chip reaches the substrate layer 11 or first binder layer 12.The generation of the thread cutting swarf that produces in the time of therefore, can preventing that substrate layer 11 is cut.As a result, can reduce the pollution of semi-conductor chip.The generation of the burr that produces in the time of in addition, also can preventing with 12 cuttings of first binder layer.
In addition, second binder layer 13 is formed by radiation curing type tackiness agent at least, and solidifies in advance by the illumination radiation line.Therefore, the bounding force of second binder layer 13 reduces than common binder layer, thereby good to the separability of adhesive layer 14.That is, second binder layer 13 plays the function of the picking up property that improves semi-conductor chip.In addition, even cutting time part is cut blade cuts, also can reduce the generation of burr.As a result, thus the border adhesive bonding agent that can not be created in second binder layer 13 and tackiness agent 14 hinders peeling off when picking up.In addition, as described radiation, can enumerate X ray, ultraviolet ray, electron rays etc.
Be provided with the zone of second binder layer 13, be preferably the inboard of the adhesive portion 18 of the cut ring on first binder layer 12.For example, as shown in Figure 2, under the planeform of second binder layer 13 was circular situation, its diameter was preferably less than the internal diameter of cut ring.Thus, first binder layer 12 has reliably that second binder layer 13 and cut ring fixed performance (being binding property) is just enough, the separability in the time of needn't considering to pick up.
Second binder layer 13 can be arranged on whole first binder layer 12, and still, as shown in Figure 1, preferably the mode with the inboard that drops into the cut ring adhesive portion is provided with.Thus, cut ring can be pasted on first binder layer 12, and needn't be arranged on second binder layer 13.Thus, the separability the when semi-conductor chip of second binder layer 13 picks up is well just enough, does not require the bond properties to cut ring.
Second binder layer 13 be on first binder layer 12, be provided with passing through the illumination radiation line and solidified binder layer in advance.When making second binder layer, 13 radiation curings by irradiation ultraviolet radiation, since the formation of crosslinking structure, the volume-diminished of second binder layer 13.Therefore, for example, when after pasting, carrying out the radiation curing of second binder layer 13, to substrate layer 11 and first binder layer, 12 stress applications, produce warpage sometimes owing to the volumetric shrinkage of second binder layer 13 with first binder layer 12.But, if be cured by radiation in advance, then can prevent from substrate layer 11 grades are applied unwanted stress, can obtain not having the semiconductor device manufacturing film of warpage.
But, also can behind the precursor (hereinafter referred to as " the second binder layer precursor ") of stacked second binder layer 13 on first binder layer 12, this second binder layer precursor illumination radiation line be made its curing, and form second binder layer 13.At this moment, can keep the adaptation between first binder layer 12 and second binder layer 13 not to be subjected to the excessively stacked state of infringement.As a result, the binding property that can suppress second tackiness agent 13 excessively reduces.In addition, also can behind stacked adhesive layer 14 on the second binder layer precursor, this second binder layer precursor illumination radiation line be made its curing, and form second binder layer 13.
As described radiation curing type tackiness agent, can use to have carbon-carbon double bond israds solidified nature functional group and show fusible tackiness agent with being not particularly limited.More specifically, as radiation curing type tackiness agent, can illustration for example in general pressure-sensitive adhesive such as described acrylic adhesives, rubber adhesive, polysiloxane-based tackiness agent, polyvinyl ether tackiness agent, cooperate radiation curing monomer component or radiation curing oligomers composition and the addition type radiation curing type tackiness agent that obtains.As described radiation curing type tackiness agent, avoid the viewpoints such as cleaning detergency electronic component, that utilize organic solvents such as ultrapure water or alcohol to clean of keeping away pollution from semiconductor wafer or glass etc. and consider, preferably with the acrylic adhesives of acrylic polymers as base polymer or polymkeric substance principal constituent.
As described acrylic polymers, preferably contain by CH by total amount with respect to acrylic polymers 2The alkyl acrylate of=CHCOOR (in the formula, R is carbonatoms 6～10, more preferably 8～9 alkyl) expression and hydroxyl monomer and do not contain the acrylic polymers that the monomer composition of carboxylic monomer constitutes.In the described alkyl acrylate, the carbonatoms of described alkyl is lower than at 6 o'clock, excessive the picking up property sometimes decline thereby peeling force becomes.On the other hand, the carbonatoms of described alkyl surpasses at 10 o'clock, and with the tackiness or the adaptation decline of adhesive layer 14, the result produces chip sometimes and disperses when cutting.
Alkyl acrylate, for example can enumerate particularly: the carbonatoms of alkyl such as Ethyl acrylate, vinylformic acid heptyl ester, Octyl acrylate, Isooctyl acrylate monomer, ethyl acrylate, vinylformic acid ester in the ninth of the ten Heavenly Stems, vinylformic acid ester in the different ninth of the ten Heavenly Stems, decyl acrylate, isodecyl acrylate is the alkyl acrylate etc. of the straight or branched of 6～10 (particularly carbonatoms is 8～9).These monomers may be used singly or two or more in combination.In addition, in the alkyl acrylate, the carbonatoms of special preferred alkyl is 8～9 alkyl acrylate, more specifically, considers from the viewpoint of picking up property, and ethyl acrylate, Isooctyl acrylate monomer, vinylformic acid ester in the different ninth of the ten Heavenly Stems are optimum.
The use level of described alkyl acrylate is preferably more than the 50 weight % with respect to the acrylic polymers total amount, more preferably 70 weight %～90 weight %.When the described use level of alkyl acrylate was lower than 50 weight %, it is excessive that peeling force becomes, picking up property decline sometimes.
In the described acrylic polymers, preferred use can with the hydroxyl monomer of described alkyl acrylate copolymer as neccessary composition.As the hydroxyl monomer, for example can enumerate: (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-2-hydroxy propyl ester, (methyl) vinylformic acid-4-hydroxyl butyl ester, (methyl) vinylformic acid-own ester of 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-hydroxyl dodecane ester, (methyl) vinylformic acid (4-methylol cyclohexyl) methyl esters etc.Described hydroxyl monomer may be used singly or two or more in combination.
The monomeric use level of described hydroxyl, with respect to the total amount of monomer component preferably in the scope of 1 weight %～30 weight %, more preferably in the scope of 3 weight %～10 weight %.When the monomeric use level of hydroxyl was lower than 1 weight %, the cohesive force of tackiness agent descended sometimes, the decline of picking up property.On the other hand, when described content surpassed 30 weight %, the polarity of tackiness agent improved sometimes, with the interaction raising of adhesive layer, picking up property decline thus.
At this, in the acrylic polymers, the alkyl acrylate acrylate in addition that can use described chemical formulation is as monomer component.As such acrylate, can enumerate other alkyl acrylate beyond the alkyl acrylate of described chemical formulation and have aromatic nucleus acrylate vinylformic acid aryl esters such as (etc.) phenyl acrylates, have the acrylate (vinylformic acid cycloalkanes ester, isobornyl acrylate etc. such as vinylformic acid ring pentyl ester, cyclohexyl acrylate) of alicyclic hydrocarbon radical etc.Such acrylate may be used singly or two or more in combination.In addition, in these materials, described other alkyl acrylate, vinylformic acid cycloalkanes ester are fit to, and can be fit to use other alkyl acrylate especially.
As described other alkyl acrylate, for example can enumerate: the carbonatoms of alkyl such as methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, vinylformic acid pentyl ester, vinylformic acid isopentyl ester is the alkyl acrylate below 5; The carbonatoms of alkyl such as vinylformic acid undecane ester, vinylformic acid dodecane ester, vinylformic acid tridecane ester, vinylformic acid tetradecane ester, vinylformic acid n-Hexadecane ester, vinylformic acid octadecane ester, vinylformic acid eicosane ester is the alkyl acrylate of (preferred 11～30) more than 11 etc.
The use level of described acrylate is preferably more than the 50 weight % with respect to the monomer component total amount, more preferably in the scope of 70 weight %～90 weight %.When the use level of acrylate was lower than 50 weight %, the peeling force of second binder layer 13 excessively increased sometimes.
Described acrylic polymers, in order to improve cohesive force and thermotolerance etc., also can contain as required with can with the corresponding unit of other monomer component of described alkyl acrylate or hydroxyl monomer copolymerization.As other monomer component that can copolymerization, for example can enumerate: methacrylic esters such as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, the secondary butyl ester of methacrylic acid, methacrylic tert-butyl acrylate; Anhydride monomers such as maleic anhydride, itaconic anhydride; Styrene sulfonic acid, allyl sulfonic acid, 2-(methyl) acrylamido-2-methyl propane sulfonic acid, (methyl) acrylamido propanesulfonic acid, (methyl) vinylformic acid sulphur propyl ester, (methyl) acryloxy naphthene sulfonic acid etc. contain the sulfonic group monomer; Acryloyl phosphoric acid-phosphorous acidic group monomers such as 2-hydroxy methacrylate; Styrene monomers such as vinylbenzene, Vinyl toluene, alpha-methyl styrene; Alkene or dienes such as ethene, divinyl, isoprene, iso-butylene; Halogen atom-containing monomers such as vinylchlorid; Contain fluorine atoms monomers such as fluorine-containing (methyl) acrylate; Acrylamide, vinyl cyanide etc.These copolymerisable monomer compositions can use one or more.The usage quantity of these copolymerisable monomers is preferably below the 40 weight % of whole monomer components.
But, in the present embodiment, do not use that to contain carboxylic monomer be very important.When use contains carboxylic monomer, the epoxy reaction in the Resins, epoxy in this carboxyl and the adhesive layer 14, second binder layer 13 improves with the tackiness of adhesive layer 14 thus, and both separabilities descend.As such carboxylic monomer that contains, can enumerate vinylformic acid, methacrylic acid, (methyl) vinylformic acid carboxylic ethyl ester, (methyl) vinylformic acid carboxylic pentyl ester, methylene-succinic acid, toxilic acid, fumaric acid, Ba Dousuan etc.
Described acrylic polymers can be by obtaining single monomer or two or more monomeric polymerization of mixtures.Polymerization also can be undertaken by the any-mode of solution polymerization (for example, radical polymerization, anionoid polymerization, cationoid polymerisation etc.), letex polymerization, mass polymerization, suspension polymerization, photopolymerization (for example, ultraviolet ray (UV) polymerization etc.) etc.From preventing that polluting clean viewpoints such as adherend considers that the content of preferred low molecular weight substance is few.Consider that from this point that the weight-average molecular weight of acrylic polymers is preferably is about 350,000～about 1,000,000, more preferably from about 450,000～about 800,000.
In addition, in order to improve the weight-average molecular weight of acrylic polymers as base polymer etc., also can suitably use outside linking agent in described second binder layer 13.As the concrete means of outside cross-linking method, can enumerate: add the method that so-called linking agents such as polyisocyanate compound, epoxy compounds, aziridine cpd, melamine class linking agent react.Use under the situation of outside linking agent, its usage quantity is according to carrying out suitably determining with the balance of the crosslinked base polymer of desire and as the use of tackiness agent.Generally with respect to below preferred 10 weight parts of described base polymer 100 weight parts, more preferably 0.1 weight part～8 weight parts.In addition, except that described composition, can also use additives such as various tackifier, antiaging agent as required in the tackiness agent.
As the described ultra-violet solidified monomer component that cooperates, for example can enumerate: 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, 1,4-butyleneglycol two (methyl) acrylate etc.In addition, ultra-violet solidified oligopolymer composition can be enumerated: various oligopolymer such as amino formate (ウ レ タ Application system), polyethers, polyester, polycarbonate-based, polybutadiene, the oligopolymer of its weight-average molecular weight in about scope of 100～about 30000 is fit to.The use level of ultra-violet solidified monomer component or oligopolymer composition can suitably determine to reduce the amount of bounding force according to the kind of described second binder layer 13.Generally speaking, for example preferred in the scope of about 5 weight parts～about 500 weight parts with respect to base polymers such as acrylic polymers 100 weight parts that constitute tackiness agent, 40 weight parts～about 150 weight parts more preferably from about.
In addition, as radiation curing type tackiness agent, except the addition type radiation curing type tackiness agent that the front illustrated, can also enumerate use in polymer lateral chain or main chain or the polymkeric substance of main chain end with carbon-carbon double bond interior as base polymer at type radiation curing type tackiness agent.Inherent type radiation curing type tackiness agent, the oligopolymer that needn't contain promising low molecular weight compositions become to grade or content few, therefore the oligopolymer composition can not passed in tackiness agent in time and move, and can form second binder layer 13 of stable layer structure, and is therefore preferred.
Described base polymer with carbon-carbon double bond can use to have carbon-carbon double bond and have fusible base polymer with being not particularly limited.As such base polymer, preferably be the base polymer of basic framework with the acrylic polymers.As the basic framework of acrylic polymers, can enumerate described illustrative (methyl) acrylic polymers.
The method of introducing carbon-carbon double bond in described acrylic polymers is not particularly limited, and can adopt the whole bag of tricks, and it is easy introducing carbon-carbon double bond from the molecular designing aspect polymer lateral chain.For example for example can enumerate: after will having the monomer and acrylic polymers copolymerization of functional group in advance, make to have the method that under the ultra-violet solidified situation that keeps carbon-carbon double bond, to carry out condensation or addition reaction with the compound of the functional group of this functional group reactions and carbon-carbon double bond with the gained multipolymer.
As the combination example of these functional groups, can enumerate: carboxylic acid group and epoxy group(ing), carboxylic acid group and '-aziridino, hydroxyl and isocyanate group etc.In the combination of these functional groups, consider the combination of preferred hydroxyl and isocyanate group from the viewpoint of easy tracking reaction.In addition, if generate described combination with (methyl) acrylic polymers of carbon-carbon double bond by the combination of these functional groups, then functional group can be on any one of acrylic polymers and described compound, under the situation that is described preferably combination, preferred acrylic polymers has hydroxyl, described compound has isocyanate group.At this moment,, for example can enumerate: methacryloyl isocyanic ester, 2-methylacryoyloxyethyl isocyanic ester, pseudoallyl-α, α-Er Jiajibianji isocyanic ester etc. as isocyanate compound with carbon-carbon double bond.In addition, as acrylic polymers, can use described illustrative hydroxyl monomer or 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, the such copolymerization such as ether compound of Diethylene Glycol mono vinyl ether are obtained (methyl) acrylic polymers.
Described inherent type ultraviolet-curing adhesive, described base polymer (particularly acrylic polymers) can be used separately, also described ultra-violet solidified monomer component or oligopolymer composition can be in the scope of not damaging characteristic, cooperated with carbon-carbon double bond.Ultra-violet solidified oligopolymer becomes to grade usually with respect to base polymer 100 weight parts in the scope of 30 weight parts, in the scope of preferred 0 weight part～10 weight parts.
By curing such as ultraviolet rays the time, contain Photoepolymerizationinitiater initiater in the described ultraviolet-curing adhesive.As Photoepolymerizationinitiater initiater, for example can enumerate: 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, Alpha-hydroxy-α, α-ketols compounds such as α '-dimethyl acetophenone, 2-methyl-2-hydroxypropiophenonepreparation, 1-hydroxycyclohexylphenylketone; Methoxyacetophenone, 2,2 '-dimethoxy-2-phenyl methyl phenyl ketone, 2,2 '-diethoxy acetophenone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-(N-morpholinyl) propane-acetophenone compounds such as 1-ketone; Benzoin ether compounds such as ethoxybenzoin, benzoin iso-propylether, anisoin methyl ether; Ketal compounds such as dibenzoyl dimethyl ketal; Aromatic sulfonyl compounds such as 2-naphthalic sulfonic chloride; 1-phenyl-1, photolytic activity oxime compoundss such as 2-propanedione-2-(O-ethoxy carbonyl) oxime; Benzophenone, benzoyl phenylformic acid, 3,3 '-dimethyl-benzophenone compounds such as 4-methoxy benzophenone; Thioxanthone, 2-clopenthixal ketone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-two clopenthixal ketones, 2,4-diethyl thioxanthone, 2, thioxanthone compounds such as 4-di-isopropyl thioxanthone; Camphorquinone; Halogenated ketone; Acylphosphine oxide; Acyl phosphonate etc.The use level of Photoepolymerizationinitiater initiater for example is about 0.05 weight part～about 20 weight parts with respect to base polymer 100 weight parts such as (methyl) acrylic polymers that constitute tackiness agent.
In addition, as ultraviolet-curing adhesive, for example can enumerate: disclosed in the Japanese kokai publication sho 60-196956 communique, comprise have that two above insatiable hungers are closed the addition polymerization compound of key, had the optical polymerism compound such as organoalkoxysilane of epoxy group(ing) and carbonyl compound, organosulfur compound, superoxide, amine, The acrylic adhesives of Photoepolymerizationinitiater initiaters such as salt compounds etc.In addition, when the illumination radiation line, cause under the obstruction solidified situation, preferably from the isolated oxygen (air) in the surface of radiation curing type second binder layer 13 at oxygen.Its method for example can be enumerated: with partition with the method for the surface coverage of described second binder layer 13 or the method etc. of in nitrogen atmosphere, carrying out the irradiation of ultraviolet israds.
The thickness of second binder layer 13 is not particularly limited, consider from the fixedly maintenance that prevents chip cutting face breach or adhesive layer 14, the viewpoint that reduces cutting swarf, preferred about 10 μ m～about 100 μ m, more preferably 15 μ m～80 μ m, further preferred 20 μ m～50 μ m.In addition, second binder layer 13 can be individual layer or multilayer.
The storage shear modulus of second binder layer 13 is preferably 5 * 10 under 23 ℃ and 150 ℃ 4Pa～1 * 10 10Pa, more preferably 1 * 10 5Pa～1 * 10 8Pa.Storage shear modulus is lower than 5 * 10 4During Pa, second binder layer 13 becomes difficult with peeling off of adhesive layer 14 sometimes.On the other hand, storage shear modulus surpasses 1 * 10 10During Pa, the adaptation between second binder layer 13 and the adhesive layer 14 descends sometimes.The storage shear modulus of second binder layer 13 is the values that obtain by the following method.That is, at first binder layer is configured as the cylindric of thick about 1.5mm, diameter 7.9mm.Then, the ARES determination of viscoelasticity device that uses the manufacturing of Rheometric Scientific company is as the Measurement of Dynamic Viscoelasticity device, second binder layer 13 is installed on the parallel plate anchor clamps, apply the shear strain of strain 0.1% (23 ℃), 0.3% (150 ℃), frequency 1Hz at shear mode, temperature is changed with 5 ℃/minute the heat-up rate temperature range at 23 ℃ to 150 ℃.By measuring the Young's modulus of this moment, can obtain the storage shear modulus under 23 ℃ and 150 ℃.In addition, second binder layer 13 is under the situation of radiation curing type, and the value of described storage shear modulus is the value behind the radiation curing.In addition, storage shear modulus for example can suitably be regulated by adding outside linking agent.
Second binder layer 13 is preferably 30mJ/m with the surface free energy of the stickup face of adhesive layer 14 2Below, more preferably 1mJ/m 2～30mJ/m 2, further preferred 15mJ/m 2～30mJ/m 2, preferred especially 20mJ/m 2～28mJ/m 2Surface free energy surpasses 30mJ/m 2The time, second binder layer 13 is excessive for the tackiness of adhesive layer 14, picking up property decline sometimes.In addition, the surface free energy of the stickup face of the second binder layer precursor and adhesive layer 14 is preferably 30mJ/m 2Below, more preferably 1mJ/m 2S～30mJ/m 2, further preferred 15mJ/m 2～30mJ/m 2, preferred especially 20mJ/m 2～28mJ/m 2Surface free energy surpasses 30mJ/m 2The time, second binder layer 13 is excessive for the tackiness of adhesive layer 14, picking up property decline sometimes.The surface free energy of second binder layer 13 or the second binder layer precursor for example can suitably be regulated by adding outside linking agent.In addition, surface free energy can calculate by the following method.That is,, make water and methylene iodide measure contact angle (θ (rad)) respectively for the surface of second binder layer 13.Then, use the surface free energy value of the contact angle determination liquid of this measured value and document record, by following formula gauging surface free energy (γ s).
γ s＝γ s d+γ s p (1)
γ L＝γ L d+γ L p (2)
(1+cosθ)γ L＝2(γ s dγ L d) 1/2+2(γ s pγ L p) 1/2 (3)
Wherein, each symbol in formula (1)～formula (3) has following implication respectively.
θ: the contact angle of measuring by the drop of water or methylene iodide (rad)
γ s: the surface free energy (mJ/m of second binder layer 13 2)
γ s d: the dispersion component (mJ/m in the surface free energy of second binder layer 13 2)
γ s p: the polar component (mJ/m in the surface free energy of second binder layer 13 2)
γ L: the surface free energy (mJ/m of water or methylene iodide 2)
γ L d: the dispersion component (mJ/m in the surface free energy of water or methylene iodide 2)
γ L p: the polar component (mJ/m in the surface free energy of water or methylene iodide 2)
In addition, the value of the surface free energy of document record is as described below.
Water: dispersion component (γ L d) 21.8mJ/m 2, polar component (γ L p) 51.0mJ/m 2
Methylene iodide: dispersion component (γ L d) 49.5mJ/m 2, polar component (γ L p) 1.3mJ/m 2
In addition, the water on the stickup face of second binder layer 13 and adhesive layer 14 and the measurement of contact angle of methylene iodide are the values that obtains by following.That is,, under the environment of 23 ± 2 ℃ of temperature, relative humidity 50 ± 5%Rh, drip the water (distilled water) of about 1 μ L or the drop of methylene iodide to the surface of second binder layer 13 according to JIS Z8703.Then, use surface contact angle meter " CA-X " (manufacturing of FACE company) after dripping 30 seconds, to measure contact angle by 3 methods (use mean value).
In addition, in the scope of not damaging effect of the present invention, also can comprise various additives (for example, tinting material, thickening material, extender, weighting agent, tackifier, softening agent, antiaging agent, antioxidant, tensio-active agent, linking agent etc.) in second binder layer 13.
Substrate layer 11, first binder layer 12 and second binder layer 13 are piled up the works that forms, and the flexural rigidity S that is calculated by E * I is preferably 5.0 * 10 4～7.0 * 10 5Scope in (wherein, I is with b * T 3The cross section second moments of/12 expressions, b is the width 10 (mm) of the test film of described works, T is the thickness (mm) of described works, E is the stretching energy storage Young's modulus (Pa) under 25 ℃ of described works).Described flexural rigidity S is more preferably 6.0 * 10 4～6.0 * 10 5Scope in, further preferably 7.0 * 10 4～5.0 * 10 5Scope in.By described flexural rigidity S is set at 5.0 * 10 4More than, can keep the rigidity of described works, when pasting, can under the situation that does not produce the pleat folding, paste wafer.On the other hand, by described flexural rigidity S is set at 7.0 * 10 5Below, described works is crooked rightly when picking up, and can realize stable picking up.At this, the modulus in tension (Pa) under 25 ℃ of described works is to use Measurement of Dynamic Viscoelasticity device (RSA-III, Rheometrics Scientific company makes) to heat up with 5 ℃/minute and measures the value that obtains.
[adhesive layer]
Adhesive layer 14 is arranged on second binder layer 13, is the layer that semiconductor wafer etc. is had gluing function.As shown in Figure 2, the second circular binder layer 13 is arranged under the situation of inboard of the cut ring adhesive portion 18 on first binder layer 12, the planeform of preferred adhesives layer 14 also is circular, and is arranged on respect to the center of second binder layer 13 and becomes concentrically ringed position substantially.In addition, the planeform of preferred adhesives layer 14 is greater than second binder layer 13, and is provided with in the mode that covers whole second binder layer 13.Thus, the periphery 14a of adhesive layer 14 (the oblique line portion zone among Fig. 2) can be layered on first binder layer 12.If such stepped construction, the periphery that then obtains adhesive layer 14 is not a gluing securely structure on second binder layer of lightly peeling off 13 but on first binder layer 12.As a result, for example, can prevent from during cutting that adhesive layer 14 from peeling off and producing from second binder layer 13 to crispatura.
As the constituent material of adhesive layer 14, can enumerate material with thermoplastic resin and thermosetting resin and usefulness.In addition, thermoplastic resin or thermosetting resin also can use separately.In addition, the stepped construction of adhesive layer 14 is not particularly limited, and for example can enumerate: the structure that is made of individual layer only perhaps forms the structure of the multilayered structure of adhesive layer on the single face of core or two sides.As described core, can enumerate film (for example, Kapton, polyester film, pet film, PEN film, polycarbonate film etc.), by glass fibre or plastics system non-woven fibre enhanced resin substrates, silicon substrate or glass substrate etc.
As described thermoplastic resin, can enumerate natural rubber, isoprene-isobutylene rubber, synthetic polyisoprene, chloroprene rubber, vinyl-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, polybutadiene, polycarbonate resin, thermoplastic polyimide resin, nylon 6 or saturated polyester resin, polyamide-imide resin or fluorine resins etc. such as nylon 6,6 polyamide resins such as grade, phenoxy resin, acrylic resin, PET or PBT.These thermoplastic resins may be used singly or two or more in combination.In these thermoplastic resins, special preferred ion impurity is few, thermotolerance is high, can guarantee the acrylic resin of the reliability of semiconductor element.
As described acrylic resin, for example can enumerate: with one or more esters with carbonatoms below 30, particularly acrylic or methacrylic acid of the straight or branched alkyl of carbonatoms 4～18 is polymkeric substance of composition etc.As described alkyl, for example can enumerate: 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 dodecyl etc.
In addition, other monomer as forming described polymkeric substance is not particularly limited, and for example can enumerate: vinylformic acid, methacrylic acid, vinylformic acid carboxylic ethyl ester, vinylformic acid carboxylic pentyl ester, methylene-succinic acid, toxilic acid, fumaric acid or Ba Dousuan etc. contain carboxylic monomer; Anhydride monomers such as maleic anhydride or itaconic anhydride; Hydroxyl monomers such as (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-2-hydroxy propyl ester, (methyl) vinylformic acid-4-hydroxyl butyl ester, (methyl) vinylformic acid-own ester of 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-hydroxyl lauryl or vinylformic acid (4-methylol cyclohexyl) methyl esters; Styrene sulfonic acid, allyl sulfonic acid, 2-(methyl) acrylamido-2-methyl propane sulfonic acid, (methyl) acrylamido propanesulfonic acid, (methyl) vinylformic acid sulphur propyl ester or (methyl) acryloxy naphthene sulfonic acid etc. contain the sulfonic group monomer; Perhaps acryloyl phosphoric acid-phosphorous acidic group monomers such as 2-hydroxy methacrylate.These materials can use separately or can be used in combination.
In addition, as described acrylic resin, preferred acrylic copolymer.Be not particularly limited as the monomer component that uses in this acrylic copolymer, for example can enumerate: butyl acrylate, ethyl propenoate etc.Among the present invention, preferably comprise butyl acrylate in 10 weight %～60 weight % scopes and the ethyl propenoate in 40 weight %～90 weight % scopes and the multipolymer that constitutes with respect to whole monomer components.
In addition, as being not particularly limited, can enumerate for example vinyl cyanide etc. with other monomer component of described monomer component copolymerization.But the usage quantity of the monomer component of these copolymerization, with respect to whole monomer components preferably in the scope of 1 weight %～20 weight %.By containing other monomer component in this numerical range, can change cohesive force, tackiness etc.
Polymerization process as acrylic copolymer is not particularly limited, and for example can adopt: existing known method such as solution polymerization process, mass polymerization, suspension polymerization, emulsion polymerization.
The second-order transition temperature of described acrylic copolymer (Tg) is preferably-30 ℃～10 ℃, more preferably-25 ℃～8 ℃.By described second-order transition temperature is set at more than-30 ℃, the energy storage Young's modulus of (for example, 100 ℃～200 ℃) in the time of can guaranteeing the high temperature of adhesive layer 14.On the other hand, by being set at below 10 ℃, can show good adaptation, close property to semiconductor wafer.
The weight-average molecular weight of described acrylic copolymer is preferably more than 100,000, and more preferably 600,000～1,200,000, preferred especially 700,000～1,000,000.By weight-average molecular weight is set at more than 100,000, the tackiness during to the high temperature of adherend such as wiring substrate or semiconductor element, semiconductor wafer surface is good, and can improve thermotolerance.In addition, by weight-average molecular weight is set at below 1,200,000, can easily be dissolved in organic solvent.Weight-average molecular weight is by gel permeation chromatography (GPC), uses the polystyrene conversion value of the working curve of polystyrene standard.
As described thermosetting resin, can enumerate resol, aminoresin, unsaturated polyester resin, Resins, epoxy, urethane resin, silicone resin (シ リ コ one Application Trees fat) or thermoset polyimide resin etc.These resins may be used singly or two or more in combination.Particularly preferably corrode the poor Resins, epoxy of the ionic impurity of semiconductor element.In addition, as curing agent for epoxy resin, preferred resol.
Described Resins, epoxy, if generally the Resins, epoxy that uses as adhesive compound then is not particularly limited, for example can use: bifunctional epoxy resin or polyfunctional epoxy resin or glycolylurea type, triglycidyl isocyanurate type or glycidyl amine type epoxy resins such as bisphenol A-type, Bisphenol F type, bisphenol S type, brominated bisphenol A type, Hydrogenated Bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, fluorenes type, phenol phenolic varnish type, ortho-cresol phenolic varnish type, three hydroxyphenyl methane types, four hydroxyphenyl ethane types.These materials may be used singly or two or more in combination.In these Resins, epoxy, preferred especially phenolic resin varnish type epoxy resin, biphenyl type epoxy resin, three hydroxyphenyl methane type Resins, epoxy or four hydroxyphenyl ethane type Resins, epoxy.This be because: these Resins, epoxy reactive high with as the resol of solidifying agent, and thermotolerance etc. is good.In addition, the content of the ionic impurity etc. of corrosion semiconductor element is few in the Resins, epoxy.
In addition, described resol works as described curing agent for epoxy resin, for example can enumerate: polycarboxylated styrenes such as phenolic varnish type resol such as phenol novolac resin, phenol aralkyl resin, cresols phenolic varnish resol, tert.-butyl phenol novolac resin, nonylphenol novolac resin, resole type resol, poly(4-hydroxystyrene) etc.These materials may be used singly or two or more in combination.In these resol, the biphenyl type phenol novolac resin of preferred following chemical formulation or phenol aralkyl resin.This is because can improve the connection reliability of semiconductor device.
Figure BSA00000432777800281
(described n is 0～10 natural number).
In addition, described n is preferably 0～10 natural number, more preferably 0～5 natural number.By in described numerical range, can guarantee the flowability of adhesive layer 14.
The ratio that cooperates of described Resins, epoxy and resol for example, be that the normal mode in 0.5 equivalent～2.0 cooperates with the hydroxyl in the described resol with respect to epoxy group(ing) 1 equivalent in the described Resins, epoxy composition is preferred.In addition, more preferably 0.8 equivalent～1.2 equivalents.That is, this be because: both cooperation ratios can not carry out sufficient curing reaction, thereby the characteristic of epoxy resin cured product are easy to deterioration beyond the described scope time.
In addition, among the present invention, especially preferably use the adhesive layer of Resins, epoxy, resol and acrylic resin.Ionic impurity in these resins is few, thermotolerance is high, it is hereby ensured the reliability of semiconductor element.The proportioning of this moment, with respect to 100 parts by weight of acrylic acid resinoid compositions, the combined amount of Resins, epoxy and resol is 10 weight parts～200 weight parts.
In advance adhesive layer 14 of the present invention is carried out under the crosslinked to a certain degree situation, interpolation just can as linking agent with the polyfunctional compound of the reactions such as functional group of the molecule chain end of polymkeric substance when making.Thus, can improve the adhesive property under the high temperature, improve thermotolerance.
As described linking agent, particularly more preferably tolylene diisocyanate, diphenylmethanediisocyanate, PPDI, 1, the polyisocyanate compounds such as affixture of 5-naphthalene diisocyanate, polyvalent alcohol and vulcabond.The addition of linking agent, with respect to described polymkeric substance 100 weight parts, common preferred 0.05 weight part～7 weight parts.When the amount of linking agent surpassed 7 weight parts, adhesive power descended, and is therefore not preferred.On the other hand, when being lower than 0.05 weight part, the cohesive force deficiency, therefore not preferred.In addition, as required, also can contain other polyfunctional compounds such as Resins, epoxy with such polyisocyanate compound.
In addition, in the adhesive layer 14, can suitably cooperate inorganic filler.The cooperation of inorganic filler is given concavo-convex to the surface of adhesive layer 14.In addition, also can give electroconductibility or raising thermal conductivity, adjusting energy storage Young's modulus etc.
As described inorganic filler, for example can enumerate: the various inorganic powders that comprise metals such as ceramic-like such as silicon-dioxide, clay, gypsum, lime carbonate, barium sulfate, aluminum oxide, beryllium oxide, silicon carbide, silicon nitride, aluminium, copper, silver, gold, nickel, chromium, lead, tin, zinc, palladium, scolding tin or alloy type and carbon etc.These materials may be used singly or two or more in combination.Wherein preferably use silicon-dioxide, especially preferably use fused silica.
The median size of inorganic filler is preferably in the scope of 0.1 μ m～5 μ m, more preferably in the scope of 0.2 μ m～3 μ m.The median size of inorganic filler is during less than 0.1 μ m, and being difficult to make the Ra of described adhesive layer is more than the 0.15 μ m.On the other hand, when described median size surpasses 5 μ m, be difficult to make Ra to be lower than 1 μ m.In addition, among the present invention, also be used in combination between the inorganic filler that can median size is different mutually.In addition, median size is a value of for example utilizing luminosity formula size-grade distribution meter (HORIBA makes, a device name LA-910) to obtain.
The use level of described inorganic filler is preferably set to 20 weight parts～80 weight parts with respect to organic resin composition 100 weight parts.Preferred especially 20 weight parts～70 weight parts.When the use level of inorganic filler was lower than 20 weight parts, thermotolerance descended, and when therefore standing long-time pyritous thermal history, adhesive layer 14 solidifies sometimes, and flowability or burial descend.In addition, when surpassing 80 weight parts, the energy storage Young's modulus of adhesive layer 14 increases.Therefore, the solidified tackiness agent is difficult to relax stress sometimes, in sealing process concavo-convex burial is descended.
In addition, in the adhesive layer 14, except described inorganic filler, can suitably cooperate other additive as required.As other additive, for example can enumerate: fire retardant, silane coupling agent or ion trap agent etc.As described fire retardant, for example can enumerate: 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, for example can enumerate: β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyldiethoxysilane etc.These compounds may be used singly or two or more in combination.As described ion trap agent, for example can enumerate: hydrotalcite, bismuth hydroxide etc.These ion trap agent may be used singly or two or more in combination.
Adhesive layer 14 also can be colored as required.In the adhesive layer 14, be not particularly limited by the painted color that presents, preference is as black, blueness, redness, green etc.Adhesive layer 14 when using as die bonding film, not painted usually (but also can be painted), when using with film, painted usually as the flip-chip semiconductor back side.When painted, can from known tinting materials such as pigment, dyestuff, suitably select to use.
The thickness of adhesive layer 14 (being total thickness under the situation of duplexer) is not particularly limited, and for example, is about 5 μ m～about 100 μ m, preferred about 5 μ m～about 50 μ m.
In addition, adhesive layer of the present invention can be used as die bonding film or use with film at the flip-chip semiconductor back side.At this, flip-chip semiconductor back side film is the film that is used to protect semiconductor chip backside (back side of exposing) when by the flip-chip bond mode semi-conductor chip being installed to substrate.
[peeling force of each interlayer]
Stripping strength X between described second binder layer 13 and the adhesive layer 14 is preferably in the scope of 0.01N/20mm～0.2N/20mm, more preferably in the scope of 0.015N/20mm～0.18N/20mm.By described stripping strength X is set at more than the 0.01N/20mm, for example when the cutting of semiconductor wafer, can prevent to produce between the two and peel off, prevent that the chip that produces semi-conductor chip from dispersing.On the other hand, by described stripping strength X is set at below the 0.2N/20mm, even omit the irradiation process of radiation, also picking up semiconductor chip well.
In addition, the stripping strength Y between described first binder layer 12 and second binder layer 13 is preferably in the scope of 0.2N/20mm～10N/20mm, more preferably in the scope of 0.3N/20mm～9.5N/20mm.By described stripping strength Y is set at more than the 0.2N/20mm, for example, when cutting, can semiconductor wafer or semi-conductor chip is fixing reliably.In addition,, second binder layer 13 can be peeled off from first binder layer 12, can be realized utilization again as the laminate film of the carrier band that constitutes by the substrate layer 11 and first binder layer by described stripping strength Y is set at below the 10N/20mm.
The ratio (Y/X) of stripping strength Y between the stripping strength X between described second binder layer 13 and the adhesive layer 14 and first binder layer 12 and second binder layer 13 is preferably in 3～500 scope, more preferably in 4～400 the scope.By described stripping strength X is set at more than 3 with the ratio (Y/X) of stripping strength Y, peel off the border that the interface is second binder layer 13 and adhesive layer 14 in the time of can making the picking up of semi-conductor chip.On the other hand, by being set at below 500 than (Y/X) described, the chip in the time of can suppressing to cut disperses or the crispaturaing of adhesive layer, and can carry out stable cutting.
Stripping strength between described first binder layer 12 and the SUS304-BA plate is preferably in the scope of 0.2N/20mm～11N/20mm, more preferably in the scope of 0.3N/20mm～9.5N/20mm.By described stripping strength is set at more than the 0.2N/20mm, can this cut ring is gluing reliably fixing, cut well.On the other hand, by described stripping strength is set at below the 11N/20mm, when the cut ring after will using is peeled off from first binder layer 12, can be suppressed at that to produce adhesive paste on the cut ring residual.
[partition]
Described partition 15 has the function of the protecting materials of conduct protection adhesive layer 14 before supplying with practical application.Wherein, as shown in Figure 2, second binder layer 13 and adhesive layer 14 are arranged under the situation of inboard of adhesive portion 18 of cut ring, and partition 15 is also protected first binder layer 12.Base material when in addition, partition 15 can be used as adhesive layer 14 is transferred to second binder layer 13 uses.Partition 15 is peeled off when semiconductor wafer being pasted on the adhesive layer 14.As partition 15, also can use by poly-strippers such as dioctyl phthalate glycol ester (PET), polyethylene, polypropylene and fluorine-containing stripper, chain alkyl esters of acrylic acid stripper are carried out plastics film after the surface coated or paper etc.
(the semiconductor device manufacturing manufacture method of film)
Below, be that example describes the manufacture method of semiconductor device manufacturing of the present invention with film with the semiconductor device manufacturing with film 1.At first, substrate layer 11 can be made film by existing known film-forming method.As this film-forming method, can illustration for example: the casting method in calendering system embrane method, the organic solvent, the blowing extrusion molding in the enclosed system, T shape die head extrusion molding, coetrusion, dry lamination method etc.
Then, on substrate layer 11, form first binder layer 12.That is, after the formation of coating adhesive composition is filmed on the substrate layer 11, under prescribed condition, make this dried coating film (carrying out heat cross-linking as required), thereby form first binder layer 12.Be not particularly limited as coating process, can enumerate: roller coat, silk screen coating, intaglio plate coating etc.In addition, drying conditions can carry out various settings according to thickness of filming or material etc.Particularly, for example, can under the condition in 80 ℃～150 ℃ drying temperature, 0.5 minute～5 minutes the scope of time of drying, carry out.In addition, also can coating adhesive composition on the partition form film after, dry coating under described drying conditions and form first binder layer 12.Afterwards, first binder layer 12 is transferred on the substrate layer 11.
Then, on first binder layer 12, form second binder layer 13.That is, coating radiation curing type binder composition on the partition form film after, under prescribed condition,, and form the second binder layer precursor with this dried coating film (carrying out heat cross-linking as required).Be not particularly limited as coating process, can enumerate: roller coat, silk screen coating, intaglio plate coating etc.In addition, drying conditions can carry out various settings according to thickness of filming or material etc.Particularly, for example, can under the condition in 80 ℃～150 ℃ drying temperature, 0.5 minute～5 minutes the scope of time of drying, carry out.In addition, also can coating adhesive composition on the partition form film after, dry coating under described drying conditions and form the second binder layer precursor.
The second binder layer precursor illumination radiation line to such formation forms second binder layer 13 thus.Use under the situation of ultraviolet ray as radiation, its illuminate condition preferably makes its accumulation light quantity at 50mJ/cm 2～1000mJ/cm 2Scope in, more preferably at 100mJ/cm 2～800mJ/cm 2Scope in.Ultraviolet irradiation is lower than 50mJ/cm 2The time, the curing of second binder layer 13 is insufficient sometimes.As a result, the adaptation increase with adhesive layer 14 causes the decline of picking up property.In addition, picking up the back, to produce adhesive paste on adhesive layer 14 residual.On the other hand, ultraviolet irradiation surpasses 1000mJ/cm 2The time, the over cure of second binder layer 13 carries out, thus modulus in tension excessively increases, and causes extendability to descend.In addition, the bounding force excessive descent thus, when the cutting of semiconductor wafer, produces chip sometimes and disperses.
Afterwards, will solidified second binder layer 13 be transferred on first binder layer 12 by the illumination radiation line.In addition, in the present embodiment, also can be transferred to the second binder layer precursor on first binder layer 12 after, this first binder layer precursor is carried out irradiation with radiation and forms second binder layer 13.As the illuminate condition of this moment, under the situation of using ultraviolet ray as radiation, preferably make its accumulation light quantity at 50mJ/cm 2～1000mJ/cm 2Scope in, more preferably at 100mJ/cm 2～800mJ/cm 2Scope in.Ultraviolet irradiation is lower than 50mJ/cm 2The time, the curing of second binder layer 13 is insufficient sometimes.As a result, the adaptation increase with adhesive layer 14 causes the decline of picking up property.In addition, picking up the back, to produce adhesive paste on adhesive layer 14 residual.On the other hand, ultraviolet irradiation surpasses 1000mJ/cm 2The time, the over cure of second binder layer 13 carries out, thus modulus in tension excessively increases, and extendability descends.In addition, the bounding force excessive descent thus, when the cutting of semiconductor wafer, produces chip sometimes and disperses.
Then, on second binder layer 13, form adhesive layer 14.That is, the adhesive compound that is used to form adhesive layer 14 is applied on the interleaving paper to reach the thickness of regulation, under prescribed condition, carries out drying again and form adhesive layer 14.By this adhesive layer 14 is transferred on second binder layer 13, can form the semiconductor device manufacturing film 1 of present embodiment.In addition, the transfer printing of adhesive layer 14 also can be carried out the second binder layer precursor.At this moment, after adhesive layer 14 transfer printings to the second binder layer precursor illumination radiation line, thereby form second binder layer 13.The illuminate condition of the radiation of this moment can be according to situation about the second binder layer precursor being transferred on first binder layer 12.
(manufacture method of semiconductor device)
Followingly the method for using described semiconductor device manufacturing to make semiconductor device with film 1 is described with reference to Fig. 3.Fig. 3 is the diagrammatic cross-section of expression form that the semiconductor wafer of pasting on the adhesive layer of described semiconductor device manufacturing with film is cut.
At first, shown in Fig. 3 (a), crimping semiconductor wafer 21 on the adhesive layer 14 in semiconductor device manufacturing usefulness film 1 is fixed its gluing maintenance (installation procedure).This operation is carried out when extruding means such as utilizing crimping roller are pushed.The stickup condition is not particularly limited, usually can 25 ℃～80 ℃ sticking temperature, 1mm/ the second～carry out under the condition of the stickup speed of 100mm/ second, the stickup pressure of 0.05MPa～1MPa.
Then, shown in Fig. 3 (b), carry out the cutting of semiconductor wafer 21.Thus, semiconductor wafer 21 is cut into the size of regulation and panelization, forms semi-conductor chip 22.Cutting is for example carried out from circuit face one side of semiconductor wafer 21 according to ordinary method.On the adhesive portion 18 of the cut ring on first binder layer 12, be provided with cut ring 23.In addition, in this operation, the incision of cutting blade 24 is proceeded to the part of second binder layer 13, and do not reach first binder layer 12.Second binder layer 13 carries out radiation curing in advance, even therefore cut off by cutting, also can reduce the adhesive paste that produces tackiness agent on this cut surface and expose (burr).As a result, can prevent to adhere to (adhesion) between the cut surface again, thereby described later picking up can be carried out more well.In addition, the substrate layer 11 and first binder layer 12 are not cut, therefore can prevent since the thread cutting swarf that the cutting of substrate layer 11 produces with burr or carefully must form be attached to the side etc. of semi-conductor chip 22, thereby realize hanging down contaminative.In addition, also can prevent burr that the cutting owing to first binder layer 12 produces etc.The cutting unit that uses in this operation is not particularly limited, and can use existing known cutting unit.In addition, semiconductor wafer 21 is gluing fixing by adhesive layer 14, therefore can suppress the chip breach or chip disperses, and also can suppress the breakage of semiconductor wafer 21.
Then, carry out the expansion of semiconductor device manufacturing with film 1.Expansion uses existing known expanding unit to carry out.Expanding unit have can be by cut ring with the semiconductor device manufacturing with film 1 to the outer shroud of the toroidal that presses down (De one Na Star shape) and diameter less than this outer shroud and the manufacturing of support semiconductor device interior ring with film 1.
Then, shown in Fig. 3 (c),, carry out picking up of semi-conductor chip 22 for the semiconductor device manufacturing is peeled off with the fixed semi-conductor chip 22 that is adhesively fixed on the film 1.Therefore second binder layer 13 solidifies by the illumination radiation line in advance, picks up under the situation of illumination radiation line not and carries out.The method of picking up is not particularly limited, and can adopt existing known the whole bag of tricks.For example can enumerate, each semi-conductor chip 22 be pushed away with film 1 one side direction from the semiconductor device manufacturing with pin, utilize pickup device will by on the semi-conductor chip 22 that the pushes away method of picking up etc.Semiconductor device manufacturing of the present invention is with in the film 1, and second binder layer 13 is good with the separability of adhesive layer 14, and therefore, even for example reduce the pin number, the amount of pushing away on perhaps reducing also can improve yield rate ground and pick up.
The semi-conductor chip 22 that picks up is fixed to (chip join) on the adherend by adhesive layer 14 is gluing.The adherend mounting is on heat block (heat block) 9.As adherend, can enumerate the semi-conductor chip of lead frame, TAB film, substrate or making in addition etc.Adherend for example can be the deformation type adherend of easy deformation, also can be the non-deformation type adherend (semiconductor wafer etc.) that is difficult to be out of shape.
As described substrate, can use existing known substrate.In addition, as described lead frame, can use die-attach area such as Cu lead frame, 42 alloy lead wire frames or comprise organic substrate of glass epoxide, BT (bismaleimides-triazine), polyimide etc.But, the invention is not restricted to these, be also included within semiconductor element be installed, be electrically connected the operable circuitry substrate in back with semiconductor element.
Adhesive layer 14 is under the situation of heat curing-type, by being heating and curing, with semi-conductor chip 22 gluing being fixed on the adherend, high-temperature capability is improved.In addition, semi-conductor chip 22 is gone up the material that obtains by the gluing substrate etc. of being fixed to of adhesive layer 14, can supply with the reflow soldering operation.Afterwards, carry out with bonding wire the wire bond that the front end of the portion of terminal (inner lead) of substrate is electrically connected with electrode pad on the semi-conductor chip 22 is sealed semi-conductor chip with sealing resin again, and with sealing resin after fixing.Thus, make the semiconductor device of present embodiment.
Embodiment
Below, the preferred embodiments of the present invention are carried out detailed illustrating.But the record of short of special qualifications such as material of putting down in writing among this embodiment or use level then only is not defined in this with scope of the present invention.
(embodiment 1)
The making of＜the second binder layer 〉
In reaction vessel with prolong, nitrogen ingress pipe, thermometer and whipping appts, add ethyl acrylate (2EHA): 80 weight parts, 2-Hydroxy ethyl acrylate (HEA): 20 weight parts and toluene: 65 weight parts, in nitrogen gas stream,, obtain acrylic polymers X 61 ℃ of aggregation processing of carrying out 6 hours.
In this acrylic polymers X:100 weight part, add 2-methylacryoyloxyethyl isocyanic ester (MOI): 24.1 weight parts (is 90 moles of % with respect to HEA), in air draught, carry out addition reaction in 48 hours and handle, obtain acrylic polymers Y at 50 ℃.
Then, in acrylic polymers Y:100 weight part, add polyisocyanate compound (trade(brand)name " コ ロ ネ one ト L ", Nippon Polyurethane Industry Co., Ltd. makes): 3 weight parts and Photoepolymerizationinitiater initiater (trade(brand)name " Irgacure 651 ", Ciba Co., Ltd. makes) 5 weight parts, the preparation binder solution.
With the binder solution of preparation in described be applied to thickness 50 μ m PET films on the face that polysiloxane is handled, 80 ℃ of following heat cross-linkings 3 minutes, form the second binder layer precursor of the radiation curing type of thickness 30 μ m, afterwards, use ultraviolet ray (UV) irradiating unit (trade(brand)name " UM-810 ", day eastern smart machine Co., Ltd. makes), with uviolizing accumulation light quantity: 300mJ/cm 2Irradiation ultraviolet radiation is made second binder layer.
The making of＜adhesive layer 〉
(Nippon Kayaku K. K makes with Resins, epoxy, trade(brand)name: EPPN501HY) 50 weight parts, resol is (bright and change into Co., Ltd. and make, trade(brand)name: MEH7800) 50 weight parts, (ノ ガ ワ ケ ミ カ Le Co., Ltd. makes acrylic copolymer, trade(brand)name: レ PVC タ Le AR31, weight-average molecular weight 700,000, second-order transition temperature-15 ℃) 100 weight parts and as the preparing spherical SiO 2 of filler (ア De マ テ Star Network ス Co., Ltd. makes, trade(brand)name: SO-25R, median size 0.5 μ m) 70 weight parts are dissolved in the methylethylketone, obtain the adhesive compound solution of concentration 23.6 weight %.
This adhesive compound solution coat is handled on the film (release liner) to the demoulding that the pet film of the thickness 50 μ m after polysiloxane stripping is handled constitutes, then 130 ℃ of dryings 2 minutes.Thus, make the adhesive layer of thickness 25 μ m.
＜semiconductor device manufacturing the making of film 〉
As the carrier band that on substrate layer, is laminated with first binder layer, the trade(brand)name S-400X that uses Nitto Denko Corp to make.On first binder layer of this carrier band, paste second binder layer that cuts out to 315mm φ at normal temperatures.Afterwards, be that the mode that the adhesive layer of 330mm φ covers second binder layer is fully pasted at 40 ℃ to cut out, make the semiconductor device manufacturing film of present embodiment.
(embodiment 2)
In the present embodiment, as the carrier band that on substrate layer, is laminated with first binder layer, the trade(brand)name CB-700 that uses Nitto Denko Corp to make, in addition, operation similarly to Example 1, the semiconductor device manufacturing film of making present embodiment.
(embodiment 3)
In the present embodiment, as the carrier band that on substrate layer, is laminated with first binder layer, the trade(brand)name M-4001 that uses Nitto Denko Corp to make, in addition, operation similarly to Example 1, the semiconductor device manufacturing film of making present embodiment.
(embodiment 4)
In the present embodiment, as the carrier band that on substrate layer, is laminated with first binder layer, the trade(brand)name HR-4011 that uses Nitto Denko Corp to make, in addition, operation similarly to Example 1, the semiconductor device manufacturing film of making present embodiment.
(embodiment 5)
In the present embodiment, as the carrier band that on substrate layer, is laminated with first binder layer, the trade(brand)name V8-S that uses Nitto Denko Corp to make, in addition, operation similarly to Example 1, the semiconductor device manufacturing film of making present embodiment.
(embodiment 6)
In the present embodiment, as the carrier band that on substrate layer, is laminated with first binder layer, the trade(brand)name UE-1088J that uses Nitto Denko Corp to make, in addition, operation similarly to Example 1, the semiconductor device manufacturing film of making present embodiment.
(embodiment 7)
In the present embodiment, as the carrier band that on substrate layer, is laminated with first binder layer, the trade(brand)name UB-2130E that uses Nitto Denko Corp to make, in addition, operation similarly to Example 1, the semiconductor device manufacturing film of making present embodiment.
(embodiment 8)
The making of＜the second binder layer 〉
In reaction vessel with prolong, nitrogen ingress pipe, thermometer and whipping appts, add ethyl acrylate (2EHA): 80 weight parts, 2-Hydroxy ethyl acrylate (HEA): 20 weight parts and toluene: 65 weight parts, in nitrogen gas stream,, obtain acrylic polymers X 61 ℃ of aggregation processing of carrying out 6 hours.
In this acrylic polymers X:100 weight part, add 2-methylacryoyloxyethyl isocyanic ester (MOI): 24.1 weight parts (is 90 moles of % with respect to HEA), in air draught, carry out addition reaction in 48 hours and handle, obtain acrylic polymers Y at 50 ℃.
Then, in acrylic polymers Y:100 weight part, add polyisocyanate compound (trade(brand)name " コ ロ ネ one ト L ", Nippon Polyurethane Industry Co., Ltd. makes): 8 weight parts and Photoepolymerizationinitiater initiater (trade(brand)name " Irgacure 651 ", Ciba Co., Ltd. makes) 5 weight parts, the preparation binder solution.
With the binder solution of preparation in described be applied to thickness 50 μ m PET films on the face that polysiloxane is handled, 80 ℃ of following heat cross-linkings 3 minutes, form the second binder layer precursor of the radiation curing type of thickness 30 μ m, afterwards, use ultraviolet ray (UV) irradiating unit (trade(brand)name " UM-810 ", day eastern smart machine Co., Ltd. makes), with uviolizing accumulation light quantity: 300mJ/cm 2Irradiation ultraviolet radiation is made second binder layer.
The making of＜adhesive layer 〉
About the adhesive layer of present embodiment, use adhesive layer similarly to Example 1.
＜semiconductor device manufacturing the making of film 〉
As the carrier band that on substrate layer, is laminated with first binder layer, use carrier band similarly to Example 1.On first binder layer of this carrier band, paste second binder layer that cuts out to 315mm φ at normal temperatures.Afterwards, be that the mode that the adhesive layer of 330mm φ covers second binder layer is fully pasted at 40 ℃ to cut out, make the semiconductor device manufacturing film of present embodiment.
(embodiment 9)
The making of＜the second binder layer precursor 〉
In reaction vessel with prolong, nitrogen ingress pipe, thermometer and whipping appts, add ethyl acrylate (2EHA): 80 weight parts, 2-Hydroxy ethyl acrylate (HEA): 20 weight parts and toluene: 65 weight parts, in nitrogen gas stream,, obtain acrylic polymers X 61 ℃ of aggregation processing of carrying out 6 hours.
In this acrylic polymers X:100 weight part, add 2-methylacryoyloxyethyl isocyanic ester (MOI): 24.1 weight parts (is 90 moles of % with respect to HEA), in air draught, carry out addition reaction in 48 hours and handle, obtain acrylic polymers Y at 50 ℃.
Then, in acrylic polymers Y:100 weight part, add polyisocyanate compound (trade(brand)name " コ ロ ネ one ト L ", Nippon Polyurethane Industry Co., Ltd. makes): 5 weight parts and Photoepolymerizationinitiater initiater (trade(brand)name " Irgacure 651 ", Ciba Co., Ltd. makes) 5 weight parts, the preparation binder solution.
With the binder solution of preparation in described be applied to thickness 50 μ m PET films on the face that polysiloxane is handled, 80 ℃ of following heat cross-linkings 3 minutes, form the second binder layer precursor of the radiation curing type of thickness 30 μ m.
The making of＜adhesive layer 〉
About the adhesive layer of present embodiment, use adhesive layer similarly to Example 1.
＜semiconductor device manufacturing the making of film 〉
As the carrier band that on substrate layer, is laminated with first binder layer, use carrier band similarly to Example 1.On first binder layer of this carrier band, paste the second binder layer precursor that cuts out to 315mm φ at normal temperatures.Afterwards, be that the mode that the adhesive layer of 330mm φ covers the second binder layer precursor is fully pasted at 40 ℃ to cut out.Then, use ultraviolet ray (UV) irradiating unit (trade(brand)name " UM-810 ", day eastern smart machine Co., Ltd. makes), accumulate light quantity from substrate layer one side with uviolizing: 300mJ/cm 2To the second binder layer precursor irradiation ultraviolet radiation, form second binder layer.Thus, make the semiconductor device manufacturing film of present embodiment.
(embodiment 10)
The making of＜the second binder layer 〉
About second binder layer of present embodiment, use second binder layer similarly to Example 1.
The making of＜adhesive layer 〉
(Nippon Kayaku K. K makes with Resins, epoxy, trade(brand)name: EPPN501HY) 200 weight parts, resol is (bright and change into Co., Ltd. and make, trade(brand)name: MEH7800) 200 weight parts, (ノ ガ ワ ケ ミ カ Le Co., Ltd. makes acrylic copolymer, trade(brand)name: レ PVC タ Le AR31, weight-average molecular weight 700,000, second-order transition temperature-15 ℃) 100 weight parts and as the preparing spherical SiO 2 of filler (ア De マ テ Star Network ス Co., Ltd. makes, trade(brand)name: SO-25R, median size 0.5 μ m) 200 weight parts are dissolved in the methylethylketone, obtain the adhesive compound solution of concentration 23.6 weight %.
This adhesive compound solution coat is handled on the film (release liner) to the demoulding that the pet film of the thickness 50 μ m after polysiloxane stripping is handled constitutes, then 130 ℃ of dryings 2 minutes.Thus, make the adhesive layer of thickness 25 μ m.
＜semiconductor device manufacturing the making of film 〉
As the carrier band that on substrate layer, is laminated with first binder layer, use carrier band similarly to Example 1.On first binder layer of this carrier band, paste second binder layer that cuts out to 315mm φ at normal temperatures.Afterwards, be that the mode that the adhesive layer of 330mm φ covers second binder layer is fully pasted at 40 ℃ to cut out, make the semiconductor device manufacturing film of present embodiment.
(embodiment 11)
The making of＜the second binder layer 〉
About second binder layer of present embodiment, use second binder layer similarly to Example 8.
The making of＜adhesive layer 〉
About the adhesive layer of present embodiment, use adhesive layer similarly to Example 10.
＜semiconductor device manufacturing the making of film 〉
As the carrier band that on substrate layer, is laminated with first binder layer, use carrier band similarly to Example 1.On first binder layer of this carrier band, paste second binder layer that cuts out to 315mm φ at normal temperatures.Afterwards, be that the mode that the adhesive layer of 330mm φ covers second binder layer is fully pasted at 40 ℃ to cut out, make the semiconductor device manufacturing film of present embodiment.
(embodiment 12)
The making of＜the second binder layer precursor 〉
About the second binder layer precursor of present embodiment, use the second binder layer precursor similarly to Example 8.
The making of＜adhesive layer 〉
About the adhesive layer of present embodiment, use adhesive layer similarly to Example 10.
＜semiconductor device manufacturing the making of film 〉
As the carrier band that on substrate layer, is laminated with first binder layer, use carrier band similarly to Example 1.On first binder layer of this carrier band, paste second binder layer that cuts out to 315mm φ at normal temperatures.Afterwards, to cut out is that the mode that the adhesive layer of 330mm φ covers the second binder layer precursor is fully pasted at 40 ℃, then, use ultraviolet ray (UV) irradiating unit (trade(brand)name " UM-810 ", day eastern smart machine Co., Ltd. makes), accumulate light quantity from substrate layer one side with uviolizing: 300mJ/cm 2To the second binder layer precursor irradiation ultraviolet radiation, form second binder layer.Thus, make the semiconductor device manufacturing film of present embodiment.
(embodiment 13)
The making of＜the second binder layer precursor 〉
About the second binder layer precursor of present embodiment, use the second binder layer precursor similarly to Example 9.
The making of＜adhesive layer 〉
About the adhesive layer of present embodiment, use adhesive layer similarly to Example 1.
＜semiconductor device manufacturing the making of film 〉
As the carrier band that on substrate layer, is laminated with first binder layer, use carrier band similarly to Example 1.On first binder layer of this carrier band, paste the second binder layer precursor that cuts out to 315mm φ at normal temperatures.Afterwards, to cut out is that the mode that the adhesive layer of 330mm φ covers the second binder layer precursor is fully pasted at 40 ℃, then, use ultraviolet ray (UV) irradiating unit (trade(brand)name " UM-810 ", day eastern smart machine Co., Ltd. makes), accumulate light quantity from substrate layer one side with uviolizing: 300mJ/cm 2To the second binder layer precursor irradiation ultraviolet radiation, form second binder layer.Thus, make the semiconductor device manufacturing film of present embodiment.
(embodiment 14)
The making of＜the second binder layer precursor 〉
In reaction vessel with prolong, nitrogen ingress pipe, thermometer and whipping appts, add ethyl acrylate (2EHA): 80 weight parts, 2-Hydroxy ethyl acrylate (HEA): 20 weight parts and toluene: 65 weight parts, in nitrogen gas stream,, obtain acrylic polymers X 61 ℃ of aggregation processing of carrying out 6 hours.
In this acrylic polymers X:100 weight part, add 2-methylacryoyloxyethyl isocyanic ester (MOI): 24.1 weight parts (is 90 moles of % with respect to HEA), in air draught, carry out addition reaction in 48 hours and handle, obtain acrylic polymers Y at 50 ℃.
Then, in acrylic polymers Y:100 weight part, add polyisocyanate compound (trade(brand)name " コ ロ ネ one ト L ", Nippon Polyurethane Industry Co., Ltd. makes): 8 weight parts and Photoepolymerizationinitiater initiater (trade(brand)name " Irgacure 651 ", Ciba Co., Ltd. makes) 5 weight parts, the preparation binder solution.
With the binder solution of preparation in described be applied to thickness 50 μ m PET films on the face that polysiloxane is handled, 80 ℃ of following heat cross-linkings 3 minutes, form the second binder layer precursor of the radiation curing type of thickness 30 μ m.
The making of＜adhesive layer 〉
About the adhesive layer of present embodiment, use adhesive layer similarly to Example 1.
＜semiconductor device manufacturing the making of film 〉
As the carrier band that on substrate layer, is laminated with first binder layer, the trade(brand)name S-400X that uses Nitto Denko Corp to make.On first binder layer of this carrier band, paste the second binder layer precursor that cuts out to 315mm φ at normal temperatures.Afterwards, use ultraviolet ray (UV) irradiating unit (trade(brand)name " UM-810 ", day eastern smart machine Co., Ltd. makes), accumulate light quantity from substrate layer one side with uviolizing: 300mJ/cm 2To the second binder layer precursor irradiation ultraviolet radiation, form second binder layer.Afterwards, be that the mode that the adhesive layer of 330mm φ covers second binder layer is fully pasted at 40 ℃ to cut out, make the semiconductor device manufacturing film of present embodiment.
(comparative example 1)
In this comparative example, use OPP film (biaxial stretch-formed polypropylene film, the manufacturing of Off タ system ラ KCC, trade(brand)name: FBS-6) replace second binder layer, operate similarly to Example 1 in addition, make the semiconductor device manufacturing film of this comparative example.
(comparative example 2)
In this comparative example, use PE film (polyethylene film, Wangzi Special Paper Co., Ltd manufacturing, the trade(brand)name: 40RL-02) replace second binder layer of surface after polysiloxane is handled, operate similarly to Example 1 in addition, make the semiconductor device manufacturing film of this comparative example.In addition, the stickup face with the adhesive layer stickup in the described PE film is the face after polysiloxane is handled.
(comparative example 3)
In this comparative example, the semiconductor device manufacturing film of described embodiment 1 in addition, is operated with this embodiment equally for not have the structure of second binder layer, makes the semiconductor device manufacturing film of this comparative example.That is, on first binder layer of carrier band, do not paste second binder layer, but under 40 ℃, only paste the adhesive layer that cuts out to 330mm φ, make semiconductor device manufacturing film.
(comparative example 4)
The making of＜the second binder layer 〉
In reaction vessel with prolong, nitrogen ingress pipe, thermometer and whipping appts, add ethyl acrylate (2EHA): 80 weight parts, 2-Hydroxy ethyl acrylate (HEA): 20 weight parts and toluene: 65 weight parts, in nitrogen gas stream,, obtain acrylic polymers X 61 ℃ of aggregation processing of carrying out 6 hours.
In this acrylic polymers X:100 weight part, add 2-methylacryoyloxyethyl isocyanic ester (MOI): 24.1 weight parts (is 90 moles of % with respect to HEA), in air draught, carry out addition reaction in 48 hours and handle, obtain acrylic polymers Y at 50 ℃.
Then, in acrylic polymers Y:100 weight part, add polyisocyanate compound (trade(brand)name " コ ロ ネ one ト L ", Nippon Polyurethane Industry Co., Ltd. makes): 5 weight parts and Photoepolymerizationinitiater initiater (trade(brand)name " Irgacure 651 ", Ciba Co., Ltd. makes) 5 weight parts, the preparation binder solution.
With the binder solution of preparation in described be applied to thickness 50 μ m PET films on the face that polysiloxane is handled, 80 ℃ of following heat cross-linkings 3 minutes, form second binder layer of the radiation curing type of thickness 30 μ m.
The making of＜adhesive layer 〉
About the adhesive layer of this comparative example, use adhesive layer similarly to Example 9.
＜semiconductor device manufacturing the making of film 〉
As the carrier band that on substrate layer, is laminated with first binder layer, use carrier band similarly to Example 1.On first binder layer of this carrier band, paste the second binder layer precursor that cuts out to 315mm φ at normal temperatures.Afterwards, be that the mode that the adhesive layer of 330mm φ covers second binder layer is fully pasted at 40 ℃ to cut out, thus, make the semiconductor device manufacturing film of this comparative example.
(comparative example 5)
In this comparative example, as the carrier band that is laminated with first binder layer on substrate layer, the trade(brand)name GE-300 that uses Nitto Denko Corp to make in addition, operates equally with comparative example 4, makes the semiconductor device manufacturing film of this comparative example.
(comparative example 6)
In this comparative example, as the carrier band that is laminated with first binder layer on substrate layer, the trade(brand)name BT-315S that uses Nitto Denko Corp to make in addition, operates equally with comparative example 4, makes the semiconductor device manufacturing film of this comparative example.
(stripping strength between second binder layer and the adhesive layer)
Cut out the sample of long 100mm * wide 20mm with film by the semiconductor device manufacturing of each embodiment and comparative example making.Then, (Nitto Denko Corp makes, trade(brand)name: BT-315), adhesive layer is strengthened to paste band on the surface of adhesive layer at normal temperatures.In addition, second binder layer and adhesive layer are clamped, (Shimadzu Scisakusho Ltd makes, trade(brand)name: AGS-J) measure stripping strength between the two to use tensile testing machine.Under peeling rate 300mm/ minute, the stripping conditions of 25 ℃ of temperature, relative humidity 50%Rh, carry out.
(peeling force between first binder layer and second binder layer)
The semiconductor device manufacturing of making from each embodiment and comparative example is with on the film adhesive layer being peeled off.Then, each the semiconductor device manufacturing after being peeled off by adhesive layer cuts out the sample of long 100mm * wide 20mm with film.Then, (Nitto Denko Corp makes, trade(brand)name: BT-315), second binder layer is strengthened at the surperficial Continuous pressing device for stereo-pattern of second binder layer at normal temperatures.In addition, second binder layer and first binder layer are clamped, use tensile testing machine (Shimadzu Scisakusho Ltd's system, trade(brand)name: AGS-J) mensuration stripping strength between the two.Under peeling rate 300mm/ minute, the stripping conditions of 25 ℃ of temperature, relative humidity 50%Rh, carry out.
(peeling force between first binder layer and SUS)
The semiconductor device manufacturing of making from each embodiment and comparative example is with on the film adhesive layer and second binder layer being peeled off.Then, each the semiconductor device manufacturing after being peeled off by the adhesive layer and second binder layer cuts out the sample of long 100mm * wide 20mm with film.Then, use the roller of 2kg to paste the SUS-304BA plate on the surface of first binder layer.Afterwards, first binder layer and SUS304-BA plate holder is tight, use tensile testing machine (Shimadzu Scisakusho Ltd's system, trade(brand)name: AGS-J) mensuration stripping strength between the two.Under peeling rate 300mm/ minute, the stripping conditions of 25 ℃ of temperature, relative humidity 50%Rh, carry out.
(ring adhibit quality)
Use each embodiment and comparative example semiconductor device manufacturing film separately, the cut ring adhibit quality is estimated by following main points.
, paste in its first binder layer top roll crimping cut ring under 25 ℃ with after on the film partition being peeled off from the semiconductor device manufacturing.At this moment, the average evaluation that the average evaluation that can paste under the situation that does not produce gauffer is zero, will produce gauffer for *, the ring adhibit quality is estimated.The result is shown in table 1～table 3.
(re-workability)
Use each embodiment and comparative example semiconductor device manufacturing film separately, re-workability is estimated by following main points.
, paste in its first binder layer top roll crimping cut ring under 25 ℃ with after on the film partition being peeled off from the semiconductor device manufacturing.By being pasted with the semiconductor device manufacturing with on the ring of film the semiconductor device manufacturing being peeled off with film, to encircle the average evaluation that the first binder layer residue (adhesive paste is residual) arranged unconfirmed and be zero, with the average evaluation of confirming to have this residue for *, re-workability is estimated.The result is shown in table 1～table 3.
(mensuration of second-order transition temperature (Tg))
The second-order transition temperature of the acrylic copolymer that uses in each embodiment and the comparative example, use determination of viscoelasticity device (Rheometic Scientific corporate system ARES), measure by the Tan under the frequency 1Hz (G " (loss Young's modulus)/G ' (energy storage Young's modulus)) with 10 ℃/minute heat-up rates.
(wafer adhibit quality, chip disperse, chip contaminative and picking up property)
Use the semiconductor device manufacturing film separately of each embodiment and comparative example, by following main points actual carry out from the back side grinding process of semiconductor wafer to pick up operation to wafer adhibit quality, chip disperse, chip contaminative and picking up property estimate.
Semiconductor wafer (12 inches of diameters, thickness 0.6mm) is carried out grinding back surface handle, the minute surface wafer of used thickness 0.05mm is as workpiece., paste under 40 ℃ the roll-in of minute surface wafer being connected on its adhesive layer with after on the film partition being peeled off from the semiconductor device manufacturing.At this moment, the average evaluation that average evaluation that can non-wrinkled stickup is zero, will produce gauffer for *, the wafer adhibit quality is estimated.The result is shown in table 1～table 3.In addition, cut, form 20 semi-conductor chips.In the cutting, cut entirely to obtain the square chip size of 10mm.In addition, in the cutting, till reaching a half thickness of semiconductor wafer, use following cutting blade Z1.In addition, till reaching a half thickness of second binder layer, use following cutting blade Z2.In addition, according to the kind of cutting blade Z1 and Z2, the cutting condition can be carried out following change.To produce the average evaluation that the chip of semi-conductor chip disperses during cutting be zero, do not produce average evaluation that chip disperses for *, chip dispersed estimates.The result is shown in table 1～table 3.
＜grinding wafer condition 〉
Grinding attachment: デ イ ス コ company makes, DFG-8560
Semiconductor wafer: 12 inch diameters (being ground to 0.05mm) from the thickness 0.6mm back side
＜wafer is pasted condition 〉
Sticker: day eastern smart machine manufacturing, MA-3000II
Pasted velometer: 10mm/ minute
Paste pressure: 0.15MPa
Platform temperature during stickup: 40 ℃
＜cutting condition 〉
Cutting unit: デ イ ス コ company makes, DFD-6361
Cut ring: 2-12-1 (manufacturing of デ イ ス コ company)
Cutting speed in feet per minute: 30mm/ second
Cutting blade:
Z1: the NBC-ZH2030-SE27HCDD that デ イ ス コ company makes
The cutting blade rotating speed: 40,000rpm
Blade height: half of semiconductor wafer thickness
Z2: the NBC-ZH1030-SE27HCBB that デ イ ス コ company makes
The cutting blade rotating speed: 45,000rpm
Blade height: half of the thickness of second binder layer
Cutting mode: A pattern/staged cutting
The wafer chip size: 10.0mm is square
Then, the semiconductor device manufacturing is drawn with film, making each chip chamber is the expansion operation of predetermined distance.In addition, with from each semiconductor device manufacturing with substrate layer one side of film with the mode picking up semiconductor chip that pin pushes away, picking up property is estimated.Particularly, pick up 20 semi-conductor chips continuously, and with each semi-conductor chip of microscopic examination.Pickup conditions is as described below.The result who observes, the burr of the side attachment of semi-conductor chip or carefully must quantity be 0 average evaluation be zero, be 1～10 average evaluation be △, be more than 11 average evaluation for *, the chip contaminative is estimated.In addition, highly be to carry out picking up of semi-conductor chip in 0 μ m～600 mu m ranges picking up, the average evaluation that all picks up be zero, average evaluation that can not pick up for *, picking up property is estimated.The result is shown in table 1～table 3.
＜pickup conditions 〉
Pickup device: SPA-300 (new river Co., Ltd. makes)
Pin number: 5
Pin kind: diameter 0.7mm, 15 ° of the acute angle number of degrees, length 10mm, front end R350 μ m
Pick-up time: 1000 milliseconds
Pickup velocity: 5mm/ second
Pick up height: as previously mentioned
(mensuration of flexural rigidity)
Mensuration is pasted substrate layer, first binder layer and second binder layer thickness of the film (cutting film) that obtains successively.Afterwards, be cut into the 10mm width, use Measurement of Dynamic Viscoelasticity device (RSA-III, Rheometrics Scientific company makes) to measure stretching energy storage Young's modulus with 5 ℃/minute heat-up rate, and the value of the stretching energy storage Young's modulus when writing down 25 ℃ (Pa of E[unit]).And, obtain the flexural rigidity that calculates by E * I.At this, the cross section second moment of I for representing with b * T3/12, b is the thickness (mm) of cutting film for the width 10 (mm) of the test film of cutting film, T, E is the stretching energy storage Young's modulus (Pa) under 25 ℃ of cutting film.The result is shown in table 1～table 3.
(synthetic determination)
Ring adhibit quality, wafer adhibit quality, chip contaminative, chip disperse, in the evaluation result of picking up property, re-workability, even exist one * situation also be evaluated as *, all evaluation results are that zero average evaluation is zero.The result is shown in table 1～table 3.
Figure BSA00000432777800521
Figure BSA00000432777800531
(result)
From described table 1 and table 2 as can be seen, the semiconductor device manufacturing of embodiment 1～14 with film by forming the structure that on substrate layer, is disposed with first binder layer and second binder layer, thereby when cutting, can prevent that the chip of slim and large-area semi-conductor chip from dispersing.In addition, at non-cohesive burr in the side of semi-conductor chip or thin palpus, also can prevent the pollution of semi-conductor chip.In addition, during the picking up of semi-conductor chip, all semi-conductor chips can pick up well, and can confirm that separability is also good.
On the other hand, with film, use the OPP film to replace under the situation of second binder layer as the semiconductor device manufacturing of comparative example 1, because when cutting, cutting blade cut to the part of OPP film, therefore can confirm result from the OPP film cutting swarf with burr or carefully must form attached to the side of semi-conductor chip etc.Therefore in addition, poor with the separability of adhesive layer, it is bad also to produce picking up of semi-conductor chip.In addition, with film, use the PE film after polysiloxane is handled to replace under the situation of second binder layer as the semiconductor device manufacturing of comparative example 2, because when cutting, cutting blade cut to the part of PE film, therefore can confirm result from the PE film cutting swarf with burr or carefully must form attached to the side of semi-conductor chip etc.In addition, with film not under the situation to the second binder layer irradiation ultraviolet radiation, second binder layer is uncured as the semiconductor device manufacturing of comparative example 4, significantly reduces with the separability of adhesive layer, and it is bad to produce picking up of semi-conductor chip.In addition, under the semiconductor device manufacturing situation that flexural rigidity is little with film of comparative example 5, when pasting, wafer produces gauffer, and therefore bad.In addition, under the semiconductor device manufacturing situation that flexural rigidity is big with film of comparative example 6, film is not crooked when picking up, and does not produce the starting point of peeling off of the adhesive layer and second binder layer, and is therefore bad.

Claims (16)

1. a semi-conductor manufacturing film uses when semi-conductive manufacturing, and it comprises:
Substrate layer,
Be arranged on first binder layer on the described substrate layer,
Be arranged on described first binder layer and in advance second binder layer by illumination radiation line and solidified radiation curing type and
Be arranged on the adhesive layer on described second binder layer.
2. semi-conductor manufacturing film as claimed in claim 1, wherein,
Described second binder layer and adhesive layer are provided with in the mode of the inboard that drops into the cut ring adhesive portion in described first binder layer at least,
The planeform of described adhesive layer is bigger than described second binder layer, and described adhesive layer is provided with in the mode that covers whole second binder layer,
In addition, be not positioned at the periphery on described second binder layer in the described adhesive layer, be arranged on described first binder layer.
3. semiconductor device manufacturing film as claimed in claim 1, wherein,
Described substrate layer, described first binder layer and described second binder layer are piled up the works that forms, and the flexural rigidity S that is calculated by E * I is 5.0 * 10 4～7.0 * 10 5Scope in,
Wherein, I is with b * T 3The cross section second moments of/12 expressions, b is the width 10 (mm) of the test film of described works, and T is the thickness (mm) of described works, and E is the stretching energy storage Young's modulus (Pa) under 25 ℃ of described works.
4. semiconductor device manufacturing film as claimed in claim 1, wherein,
Stripping strength X between described second binder layer and the adhesive layer is in the scope of 0.01N/20mm～0.2N/20mm.
5. semiconductor device manufacturing film as claimed in claim 1, wherein,
Stripping strength Y between described first binder layer and second binder layer is in the scope of 0.2N/20mm～10N/20mm.
6. semiconductor device manufacturing film as claimed in claim 1, wherein,
The ratio (Y/X) of stripping strength Y between stripping strength X between described second binder layer and the adhesive layer and described first binder layer and second binder layer is in 3～500 scope.
7. semiconductor device manufacturing film as claimed in claim 1, wherein,
The thickness of described second binder layer is in the scope of 10 μ m～100 μ m.
8. semiconductor device manufacturing film as claimed in claim 2, wherein,
Stripping strength between described first binder layer and the SUS304-BA plate is in the scope of 0.2N/20mm～11N/20mm.
9. semiconductor device manufacturing film as claimed in claim 1, wherein,
Described second binder layer is by being formed on the binder layer on described first binder layer after the precursor cures of illumination radiation line with this second binder layer.
10. semiconductor device manufacturing film as claimed in claim 1, wherein,
Described second binder layer is to be arranged on described first binder layer by the precursor with this second binder layer to be cured the binder layer that forms by the illumination radiation line afterwards.
11. semiconductor device manufacturing film as claimed in claim 1, wherein,
Described adhesive layer is the adhesive layer that forms on solidified second binder layer by the illumination radiation line in advance.
12. semiconductor device manufacturing film as claimed in claim 1, wherein,
Described adhesive layer is arranged on by the illumination radiation line and is cured on the precursor of second binder layer before.
13. semiconductor device manufacturing film as claimed in claim 1, wherein,
Described adhesive layer is formed by Resins, epoxy, phenol resins and acrylic resin at least.
14. semiconductor device manufacturing film as claimed in claim 13, wherein,
The second-order transition temperature of described acrylic resin is in-30 ℃～10 ℃ scope.
15. semiconductor device manufacturing film as claimed in claim 1, wherein,
Described second binder layer is formed by acrylic polymers at least.
16. the manufacture method of a semiconductor device is used the described semiconductor device manufacturing thin film fabrication semiconductor device of claim 1, it is characterized in that,
Described method comprises following operation at least:
In the operation of described semiconductor device manufacturing with crimping semiconductor wafer on the described adhesive layer of film,
Thereby described semiconductor wafer is cut the operation that forms semi-conductor chip with described adhesive layer, wherein, the penetraction depth of cutting described second binder layer stop and
The operation that described semi-conductor chip is peeled off from described second binder layer with described adhesive layer, and,
Stripping process from the crimping process of described semiconductor wafer to semi-conductor chip is not to the described second binder layer illumination radiation line.
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CN105765699A (en) * 2013-11-22 2016-07-13 琳得科株式会社 Dicing-sheet base film and base-film manufacturing method
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Application publication date: 20110921