CN104745108A - Resin film for semiconductor device, and method for producing semiconductor device - Google Patents

Resin film for semiconductor device, and method for producing semiconductor device Download PDF

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Publication number
CN104745108A
CN104745108A CN201410828176.6A CN201410828176A CN104745108A CN 104745108 A CN104745108 A CN 104745108A CN 201410828176 A CN201410828176 A CN 201410828176A CN 104745108 A CN104745108 A CN 104745108A
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semiconductor device
ion
die bonding
bonding film
resin
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CN104745108B (en
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木村雄大
三隅贞仁
大西谦司
宍户雄一郎
菅生悠树
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Nitto Denko Corp
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Nitto Denko Corp
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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
    • H01L24/80—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
    • 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
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    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—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
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
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    • H01L2224/01—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
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45117—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 400°C and less than 950°C
    • H01L2224/45124—Aluminium (Al) as principal constituent
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    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—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
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45144—Gold (Au) as principal constituent
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    • H01L2224/01—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
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45147—Copper (Cu) as principal constituent
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
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    • H01L2224/01—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
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
    • 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
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • H—ELECTRICITY
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    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Abstract

The invention relates to a RESIN FILM FOR SEMICONDUCTOR DEVICE, of which the proportion of the copper ion capture rate A before thermal-curing to the copper ion capture rate B after the thermal-curing is more than 1, and relates to the producing method of the semiconductor.

Description

The semiconductor device manufacture method of resin film and semiconductor device
Technical field
The present invention relates to the manufacture method of semiconductor device resin film and semiconductor device.
Background technology
All the time, in semiconductor devices, when there will be a known, the wiring of self-forming on substrate be (such as, thin copper film), lead-in wire that substrate is electrically connected with semi-conductor chip (such as, copper goes between) produce metal ion (such as, cupric ion), cause malfunction.
Therefore, carry out the following studies in recent years: in the resin for semi-conductor chip being bonded to the substrates such as lead frame, adding the additive catching metal ion, preventing the malfunction (such as, see patent documentation 1) of semiconductor device thus.
prior art document
patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-333085 publication
Summary of the invention
the problem that invention will solve
But, in the manufacture of semiconductor device, due to through various heating process, therefore there is the worry of aforementioned additive generation thermolysis etc., the such problem of sufficient ion-catching when having, cannot be played.
The present invention makes in view of foregoing problems, its object is to, also there is the semiconductor device resin film of sufficient ion-catching after thermal history even if provide and using the manufacture method of semiconductor device of this semiconductor device resin film.
for the scheme of dealing with problems
Present inventors etc. conduct in-depth research semiconductor device resin film.Its result, finds surprisingly, in specific semiconductor device resin film, after thermofixation with thermofixation before ion-catching equal or higher than ion-catching before thermofixation after thermofixation, thus complete the present invention.
Namely, the feature of semiconductor device resin film of the present invention is, the semiconductor device resin film of the heavy 2.5g before heat of immersion in the aqueous solution 50ml with 10ppm cupric ion is solidified, and the copper ion concentration (ppm) placed at 120 DEG C in the aqueous solution after 20 hours is set to X, and the semiconductor device resin film of the heavy 2.5g of thermofixation after 5 hours at 175 DEG C will be immersed in the aqueous solution 50ml with 10ppm cupric ion, and when at 120 DEG C, the copper ion concentration (ppm) placed in the aqueous solution after 20 hours is set to Y, the cupric ion catch rate A calculated by following formula (1) is more than 1 with the ratio B/A of the cupric ion catch rate B calculated by following formula (2).
Formula (1): [(10-X)/10] × 100 (%)
Formula (2): [(10-Y)/10] × 100 (%)
According to preceding solution, the ratio B/A of the cupric ion catch rate B after the cupric ion catch rate A before thermofixation and thermofixation is more than 1, and compared with before thermofixation, after thermofixation, cation capture also can not reduce.Therefore, even if also there is sufficient ion-catching after thermal history in the manufacture of semiconductor device.
In preceding solution, 5% weightless temperature is preferably more than 200 DEG C.
When 5% weightless temperature is more than 200 DEG C, as the excellent heat resistance of semiconductor device by resin film entirety.
In preceding solution, preferably containing catching cationic inorganic ion scavenger.
The more difficult generation thermolysis of inorganic ion scavenger.Therefore, during containing inorganic ion scavenger, even if also there is ion-catching more fully after thermal history.
In preceding solution, the content of aforementioned inorganic ion capturing agent is preferably 1 ~ 30 % by weight.
By the content of aforementioned inorganic ion capturing agent is set to more than 1 % by weight, thus effectively can catching positively charged ion, by being set to less than 30 % by weight, thus good film shaped property can be obtained.
In preceding solution, in the aqueous solution 50ml of cupric ion with 10ppm, be immersed in the semiconductor device resin film of the weight 2.5g of thermofixation after 5 hours at 175 DEG C and the pH placing the aqueous solution after 20 hours at 120 DEG C is preferably in the scope of 4 ~ 6.
Inorganic ion scavenger utilizes ion-exchange to catch positively charged ion usually.Therefore, cation capture is subject to the impact of pH.Specifically, when pH excessively becomes acidity, cationic seizure sometimes reduces.Therefore, by being set in the scope of 4 ~ 6 by aforementioned pH, thus cation capture can be made better.
In addition, the feature of the manufacture method of semiconductor device of the present invention is, comprises following operation:
Prepare the operation of aforementioned semiconductor device resin film; And
Clip aforementioned semiconductor device resin film, by semi-conductor chip chip join to the chip join operation on adherend.
According to preceding solution, the ratio B/A of the cupric ion catch rate B after the cupric ion catch rate A before the thermofixation of semiconductor device resin film and thermofixation is more than 1, and compared with before thermofixation, after thermofixation, cation capture also can not reduce.Therefore, even if also there is sufficient ion-catching after thermal history in the manufacture of semiconductor device.Its result, can suppress the malfunction of manufactured semiconductor device.
Accompanying drawing explanation
Fig. 1 is the schematic cross-section of the die bonding film of the band cutting blade that an embodiment of the invention are shown.
Fig. 2 is the schematic cross-section of the die bonding film of the band cutting blade that another embodiment of the present invention is shown.
Fig. 3 is the schematic cross-section of a kind of manufacture method of semiconductor device for illustration of present embodiment.
Embodiment
Below, first, as suitable embodiment of the present invention, the situation being die bonding film for semiconductor device resin film of the present invention is described.About the die bonding film of present embodiment, the die bonding film of the state of cutting blade of not fitting in the die bonding film of the band cutting blade of following explanation can be listed.Therefore, below, the die bonding film for band cutting blade is described, and about die bonding film, is described wherein.
Fig. 1 is the schematic cross-section of the die bonding film of the band cutting blade that an embodiment of the invention are shown.Fig. 2 is the schematic cross-section of the die bonding film of another band cutting blade that another embodiment of the present invention is shown.
As shown in Figure 1, the die bonding film 10 of cutting blade is with to have the formation being laminated with die bonding film 3 on cutting blade 11.Cutting blade 11 stacked binder layer 2 and forming on base material 1, die bonding film 3 is arranged on this binder layer 2.It should be noted that, the die bonding film of band cutting blade also can for being only formed with the formation of die bonding film 3 ' the die bonding film 12 as the band cutting blade shown in Fig. 2 in workpiece attaching part.Die bonding film 3 ' is only different from die bonding film 3 shape, and the various resins, additive, filler etc. that form film can use the material same with die bonding film 3.
Below, each formation of the die bonding film 10 of the band cutting blade shown in main explanatory view 1.
(die bonding film)
About die bonding film 3, the die bonding film 3 of the heavy 2.5g before heat of immersion in the aqueous solution 50ml with 10ppm cupric ion is solidified, and the copper ion concentration (ppm) placed at 120 DEG C in the aqueous solution after 20 hours is set to X, and the die bonding film 3 of the heavy 2.5g of thermofixation after 5 hours at 175 DEG C will be immersed in the aqueous solution 50ml with 10ppm cupric ion, and when at 120 DEG C, the copper ion concentration (ppm) placed in the aqueous solution after 20 hours is set to Y, the cupric ion catch rate A calculated by following formula (1) is more than 1 with the ratio B/A of the cupric ion catch rate B calculated by following formula (2).
Formula (1): [(10-X)/10] × 100 (%)
Formula (2): [(10-Y)/10] × 100 (%)
Aforementioned is more than 1, preferably more than 1.1 than B/A.In addition, preferably aforementioned comparatively large than B/A, but be such as less than 10.The aforementioned of die bonding film 3 is more than 1 than B/A, and compared with before thermofixation, after thermofixation, cation capture also can not reduce.Therefore, even if also there is sufficient ion-catching after thermal history in the manufacture of semiconductor device.
5% weightless temperature of die bonding film 3 is preferably more than 200 DEG C, is more preferably more than 250 DEG C, more preferably more than 300 DEG C.When 5% weightless temperature of die bonding film 3 is more than 200 DEG C, as the excellent heat resistance of die bonding film 3 entirety.The method of the measuring method foundation embodiment record of 5% weightless temperature.5% weightless temperature of die bonding film 3 can be adjusted by the manufacturing condition (drying temperature after such as, applying masking, time of drying) when the selection of the resin, additive, filler etc. of formation die bonding film 3, formation die bonding film 3.
Die bonding film 3 is preferably containing catching cationic additive.Containing when catching cationic additive in die bonding film 3, easily ion-catching can be given.
As the positively charged ion caught by the cationic additive of aforementioned seizure, include, for example out Na, K, Ni, Cu, Cr, Co, Hf, Pt, Ca, Ba, Sr, Fe, Al, Ti, Zn, Mo, Mn, V plasma (positively charged ion).The cationic additive of aforementioned seizure is especially preferably the material at least catching Cu ion (cupric ion).This is because cupric ion produces than easier in a large number with other Ion Phase, and the possibility affected greatly the malfunction of semiconductor device is high.
As the cationic additive of aforementioned seizure, the complex compound can list inorganic ion scavenger, forming complex compound with positively charged ion forms compound etc.Wherein, preferred inorganic ion scavenger.This is because therefore the more difficult generation thermolysis of inorganic ion scavenger, even if also have ion-catching more fully after thermal history.
(inorganic ion scavenger)
Aforementioned inorganic ion capturing agent is for utilizing ion-exchange to catch cationic inorganic ion exchanger.Aforementioned inorganic ion capturing agent preferably can not only catch positively charged ion, can also catch the inorganic double ion trapping agent of negatively charged ion.When aforementioned inorganic ion capturing agent is double ion trapping agent, pH's is with low uncertainty.Its result, can suppress through time ion-catching reduce.Specifically, the ion (such as, hydrogen ion) that ion (such as, the hydroxide ion) neutralization discharged as counter ion when catching negatively charged ion discharges as counter ion when catching positively charged ion.Ion-catching is undertaken by balanced reaction (ion-exchange), and therefore, reduced by the concentration of counter ion, the ion-exchange of object ion is promoted.
In this specification sheets, double ion trapping agent refers to, can catch the inorganic double ion permutoid of a certain amount of above cupric ion and chlorion.As aforementioned inorganic double ion permutoid, specifically, copper (II) ionic distribution coefficient (Kd) obtained according to the measuring method of following copper (II) ionic distribution coefficient can be listed be more than 10 and be the material of more than 0.5 according to the loading capacity (meq/g) that the measuring method of following loading capacity is obtained.
The measuring method > of < copper (II) ionic distribution coefficient
In 100ml plastic containers, put into inorganic double ion permutoid 5.0g and the experimental liquid 50ml containing 0.01N copper (II) ion, cover tightly, vibrate 24 hours at 25 DEG C.After vibration, filter with the membrane filter of 0.1 μm, measure copper (II) ionic concn in filtrate with ICP-AES (manufacture of SII Nano-Technology Co., Ltd., SPS-1700HVR), thus obtain copper (II) ionic distribution COEFFICIENT K d.Kd (ml/g) is by (C 0-C) × V/ (C × m) expression, C 0for the weight (g) that initial ion concentration, C are experimental liquid ionic concn, V is experimental liquid volume (ml), m is inorganic double ion permutoid.
The measuring method > of < loading capacity
In the NaCl saturated aqueous solution of 50ml, flood the inorganic double ion permutoid of 1.0g, at room temperature place 20 hours.By the amount utilizing the titration of the HCl aqueous solution of 0.1N to carry out the hydroxide ion quantitatively produced by inorganic double ion permutoid, obtain loading capacity (meq./g).
About die bonding film 3, in the aqueous solution 50ml of cupric ion with 10ppm, be immersed in the die bonding film 3 of the weight 2.5g of thermofixation after 5 hours at 175 DEG C and the pH placing the aqueous solution after 20 hours at 120 DEG C is preferably in the scope of 4 ~ 6, is more preferably in the scope of 4.2 ~ 5.8, more preferably 4.4 ~ 5.5 scope in.Inorganic ion scavenger utilizes ion-exchange to catch positively charged ion usually.Therefore, cation capture is subject to the impact of pH.Specifically, when pH excessively becomes acidity, cationic seizure sometimes reduces.Therefore, by being set in the scope of 4 ~ 6 by aforementioned pH, cation capture can be made better.As the method be set to by aforementioned pH in the scope of 4 ~ 6, the method using following inorganic double ion trapping agent can be listed.When using inorganic double ion trapping agent, pH can be suppressed excessively to become acid, maintain higher ion-catching.
Aforementioned inorganic ion capturing agent is not particularly limited, various inorganic ion scavenger can be used, include, for example out the hydrous oxide of the element in the group being selected from and being made up of antimony, bismuth, zirconium, titanium, tin, magnesium and aluminium.These can be used alone or in combination two or more to use.Wherein, the three compositions system hydrous oxide of preferably magnesium, aluminium and zirconium.The three compositions system of magnesium, aluminium and zirconium, owing to utilizing ion-exchange to catch positively charged ion and these two kinds of ions of negatively charged ion, also can make pH remain near neutral even if therefore catch ion.Therefore, better ion-catching can be obtained.In addition, magnesium, aluminium and zirconium three compositions system require in the semiconductor applications without antimony suitable especially.
As the commercially available product of aforementioned inorganic ion capturing agent, the trade(brand)name that Toagosei Co., Ltd manufactures can be listed: IXEPLAS-A1, IXEPLAS-A2 etc.These are inorganic double ion trapping agent.
The median size of aforementioned inorganic ion capturing agent is preferably 0.1 ~ 1 μm, is more preferably 0.2 ~ 0.6 μm.By the median size of aforementioned inorganic ion capturing agent is set to less than 1 μm, specific surface area can be increased.Its result, can improve ion-catching further.In addition, by the median size of aforementioned inorganic ion capturing agent is set to less than 1 μm, can the thickness of thinned die bonding film 3.In addition, by the median size of aforementioned inorganic ion capturing agent is set to more than 0.1 μm, dispersiveness can be improved.
Aforementioned inorganic ion capturing agent has preferably carried out processing (pre-treatment) with silane coupling agent.If carried out silane coupled process, then the dispersiveness of inorganic ion scavenger has become good, and the masking of die bonding film 3 is excellent.Especially, the inorganic ion scavenger that particle diameter is little is more easily assembled, if but carry out silane coupled process, then dispersiveness becomes good.Its result, can manufacture the die bonding film 3 that thickness containing inorganic ion scavenger is thin aptly.It should be noted that, the present inventor etc. confirm, even if carry out silane coupled process to inorganic ion scavenger, compared with untreated state, cation capture is also equal or does not obviously reduce.
As silane coupling agent, the material preferably containing Siliciumatom, hydrolization group and organo-functional group.
Hydrolization group is bonded to Siliciumatom.
As hydrolization group, include, for example out methoxyl group, oxyethyl group etc.Wherein, fast for hydrolysis rate and process is easy to reason, preferred methoxyl group.
Even if from can be cross-linked with inorganic ion scavenger and the cross-linking set that silane coupling agent can be cross-linked inorganic ion scavenger surface to each other also can carry out surface-treated aspect with silane coupling agent to inorganic ion scavenger entirety less, the quantity of the hydrolization group in silane coupling agent is preferably 2 ~ 3, is more preferably 3.
Organo-functional group is bonded to Siliciumatom.
As organo-functional group, include, for example out the group comprising acryl, methacryloyl, epoxy group(ing), phenyl amino etc.Wherein, not there is reactivity, aspect that the storage stability of inorganic ion scavenger that processes is good, preferred acryl from epoxy resin.
It should be noted that, can react when having the functional group high with epoxy reaction with epoxy resin, therefore storage stability, mobility reduce.From the aspect suppressing mobility to reduce, as organo-functional group, usually preferably not containing the group of primary amino, sulfydryl or isocyanate group.
The quantity of the organo-functional group in silane coupling agent is preferably 1.Siliciumatom forms 4 keys, if therefore organo-functional group is many, then and the quantity not sufficient of hydrolysising group.
Silane coupling agent also can further containing the alkyl being bonded to Siliciumatom.By making silane coupling agent contain alkyl, reactivity can be reduced further compared with methacryloyl, the surface-treated deviation caused by violent reaction can be prevented.As alkyl, methyl, dimethyl etc. can be listed.Wherein, preferable methyl.
As silane coupling agent, specifically, 2-(3 can be listed, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl group triethoxyl silane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyl diethoxy silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, N-phenyl-3-TSL 8330, 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloyloxypropyl methyl diethoxy silane, 3-methacryloxypropyl etc.
As the method with silane coupling agent process inorganic ion scavenger, be not particularly limited, the wet method mixing inorganic ion scavenger and silane coupling agent in a solvent, the dry method etc. processing inorganic ion scavenger and silane coupling agent in the gas phase can be listed.
The treatment capacity of silane coupling agent is not particularly limited, relative to 100 parts by weight of inorganic ion capturing agents, preferably processes with 0.05 ~ 5 weight part silane coupling agent.
The content of the cationic additive of aforementioned seizure is preferably 1 ~ 30 % by weight, is more preferably 2 ~ 25 % by weight, more preferably 3 ~ 20 % by weight.By the content of cationic for aforementioned seizure additive is set to more than 1 % by weight, effectively can catching positively charged ion, by being set to less than 30 % by weight, good film shaped property can be obtained.
Die bonding film 3 preferably containing any one in thermoplastic resin and thermosetting resin or both.As foregoing thermosetting resins, resol, aminoresin, unsaturated polyester resin, epoxy resin, urethane resin, silicone resin or thermoset polyimide resin etc. can be listed.These resins can be used alone or in combination two or more to use, particularly preferably use in epoxy resin and resol at least any one.Wherein, preferably epoxy resin is used.During containing epoxy resin, at high temperature can obtain the higher bonding force of die bonding film 3 and wafer.Its result, die bonding film 3 becomes with the bonding interface of wafer and not easily intakes, and ion becomes and not easily moves.Thus, reliability improves.
As long as the resin that aforementioned epoxy resins uses usually used as adhesive composite is just not particularly limited, such as, can use the epoxy resin of difunctional epoxy resin, polyfunctional epoxy resin or the glycolylurea type of bisphenol A-type, bisphenol-f type, bisphenol S type, bmminated bisphenol-A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, fluorenes type, phenol novolak type, ortho cresol novolak type, trihydroxybenzene methylmethane type, four hydroxy phenyl ethane types etc., triglycidyl group isocyanuric acid ester type or glycidic amine type etc.These can be used alone or in combination two or more to use.In the middle of these epoxy resin, particularly preferably phenolic resin varnish type epoxy resin, biphenyl type epoxy resin, trihydroxybenzene methylmethane type resin or four hydroxy phenyl ethane type epoxy resin.This is because these epoxy resin are rich in the reactivity with the resol as solidifying agent, the excellences such as thermotolerance.
And then, aforementioned resol plays a role as the solidifying agent of aforementioned epoxy resins, include, for example out the novolak phenolics such as phenol resol resins, phenol aralkyl resin, cresol novolac resin, t-butylphenol novolac resin, nonylphenol novolac resin, resol type phenol resin, gathers polystyrene oxide etc. such as Styrene oxide 98min.s.These can be used alone or combinationally use two or more.In the middle of these resol, particularly preferably phenol resol resins, phenol aralkyl resin.This is because the connection reliability of semiconductor device can be improved.
About the compounding ratio of aforementioned epoxy resins and resol, such as, with relative to epoxy group(ing) 1 equivalent in aforementioned epoxy resins composition, the hydroxyl in resol is that to carry out compounding be suitable to the mode of 0.5 ~ 2.0 equivalent.More appropriately 0.8 ~ 1.2 equivalent.That is, this is because, when both compounding ratios depart from aforementioned range, cannot carry out sufficient curing reaction, the characteristic of epoxy resin cured product is easily deteriorated.
As aforementioned thermoplastic resin, the saturated polyester resin such as polyamide resin, phenoxy resin, acrylic resin, PET, PBT, polyamide-imide resin or the fluoro-resin etc. such as natural rubber, isoprene-isobutylene rubber, synthetic polyisoprene, chloroprene rubber, ethylene-acetate acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, polybutadiene, polycarbonate resin, thermoplastic polyimide resin, 6-nylon, 6,6-nylon can be listed.These thermoplastic resins can be used alone or combinationally use two or more.In the middle of these thermoplastic resins, particularly preferably ionic impurity is few and thermotolerance is high, can guarantee the acrylic resin of the reliability of semiconductor element.
As foregoing acrylic resin, be not particularly limited, can list the one kind or two or more polymkeric substance (acrylic copolymer) etc. of ester as monomer component with the acrylic or methacrylic acid of the alkyl of carbon number less than 30, the particularly straight or branched of carbon number 4 ~ 18.As aforesaid alkyl, include, for example out 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, as other monomer forming aforementioned polymer, be not particularly limited, include, for example out vinylformic acid, methacrylic acid, carboxy ethyl acrylate, carboxypentyl acrylate, methylene-succinic acid, toxilic acid, the carboxyl group-containing monomer of fumaric acid or β-crotonic acid etc. and so on, the anhydride monomers of maleic anhydride or itaconic anhydride etc. and so on, (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-4-hydroxybutyl, the own ester of (methyl) vinylformic acid-6-hydroxyl, (methyl) vinylformic acid-8-hydroxyl monooctyl ester, (methyl) vinylformic acid-10-hydroxyl ester in the last of the ten Heavenly stems, the hydroxyl monomer of (methyl) vinylformic acid-12-hydroxylauric ester or vinylformic acid (4-hydroxymethylcyclohexyl)-methyl esters etc. and so on, styrene sulfonic acid, allyl sulphonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic, (methyl) acrylamide propane sulfonic acid, (methyl) sulfopropyl acrylate or (methyl) propane sulfonic acid etc. and so on containing sulfonic group monomer, or the phosphorous acid-based monomers of 2-hydroxylethyl acyl phosphate etc. and so on.These can be used alone or combinationally use two or more.
As the compounding ratio of aforementioned hot curable resin, as long as the level that during heating, die bonding film 3 plays as the function of heat curing-type under prescribed conditions is just not particularly limited, is preferably in the scope of 5 ~ 60 % by weight, is more preferably in the scope of 10 ~ 50 % by weight.
Die bonding film 3 is especially preferred: containing epoxy resin, resol and acrylic resin, and relative to 100 parts by weight propylene acid resins, the total amount of epoxy resin and resol is 10 ~ 2000 weight parts, is more preferably 10 ~ 1500 weight parts, more preferably 10 ~ 1000 weight parts.Be more than 10 weight parts by making the total amount of epoxy resin and resol relative to 100 parts by weight propylene acid resins, can obtain solidifying the adhesive effect brought, can suppressing to peel off, by being below 2000 weight parts, film fragilityization can be suppressed and operability reduces.
When being cross-linked with certain level in advance by die bonding film 3, being added with the multi-functional compounds reacted with the functional group etc. of the molecule chain end of polymkeric substance is good as linking agent.Thereby, it is possible to improve adhesion properties at high temperature, realize the improvement of thermotolerance.
As aforementioned crosslinking agent, existing known material can be adopted.Especially the more preferably polyisocyanate compound such as affixture of tolylene diisocyanate, diphenylmethanediisocyanate, PPDI, 1,5-naphthalene diisocyanate, polyvalent alcohol and vulcabond.As the addition of linking agent, relative to 100 weight part aforementioned polymer, be usually preferably set to 0.05 ~ 7 weight part.By the amount of linking agent is set to below 7 weight parts, bonding force can be suppressed to reduce.In addition, by being set to more than 0.05 weight part, force of cohesion can be improved.In addition, also can as required simultaneously containing other multi-functional compounds such as epoxy resin together with this polyisocyanate compound.
In addition, can according to the suitable compounding filler of its purposes in die bonding film 3.Filler compounding makes the raising of the thermal conductivity to die bonding film 3, the adjustment etc. of modulus becomes possibility.As aforementioned filler, mineral filler and organic filler can be listed, from the view point of the characteristic such as raising, the adjustment of melt viscosity, thixotropic imparting of the raising of treatability, thermal conductivity, preferred mineral filler.As aforementioned inorganic filler, be not particularly limited, include, for example out aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesiumcarbonate, Calucium Silicate powder, Magnesium Silicate q-agent, calcium oxide, magnesium oxide, aluminum oxide, aluminium nitride, aluminium borate whisker, boron nitride, crystalline silica, soft silica etc.These can be used alone or combinationally use two or more.From the view point of the raising of thermal conductivity, preferential oxidation aluminium, aluminium nitride, boron nitride, crystalline silica, soft silica.In addition, good from the view point of the balance of above-mentioned each characteristic, preferred crystalline silica or soft silica.
The median size of aforementioned filler can be set to 0.005 ~ 10 μm.By the median size of aforementioned filler is set to more than 0.005 μm, can make to the wettability of adherend and cementability good.In addition, by being set to less than 10 μm, thus the effect in order to give the filler that above-mentioned each characteristic is added can be made abundant, and can thermotolerance be guaranteed.It should be noted that, such as in order to utilize the size-grade distribution meter of luminosity formula, (HORIBA manufactures the median size of filler, device name; LA-910) value obtained.
It should be noted that, in die bonding film 3, can also suitable other additive compounding as required except the cationic additive of aforementioned seizure.As other additive, anion catching agent, dispersion agent, antioxidant, silane coupling agent, curing catalyst etc. can be listed.These can be used alone or combinationally use two or more.
The thickness of die bonding film 3 is not particularly limited, is preferably 1 ~ 40 μm, is more preferably 3 ~ 35 μm, more preferably 5 ~ 30 μm.Thickness is less than 40 μm, time thinner, can the thickness of semiconductor device integral of this die bonding film 3 of thinning use.In addition, when thickness is more than 1 μm, good ion-catching can be played.
(cutting blade)
Cutting blade 11 has the structure being laminated with binder layer 2 on base material 1.
Base material 1 becomes the intensity parent of the die bonding film 10 of band cutting blade.Base material 1 preferably has ultraviolet perviousness.As base material 1, include, for example out Low Density Polyethylene, straight-chain polyethylene, medium-density polyethylene, high density polyethylene(HDPE), ultra-low density polyethylene, atactic copolymerized polypropene, block copolymerization polypropylene, homo-polypropylene, polybutene, the polyolefine such as polymethylpentene, ethylene-acetate acetate copolymer, ionomer resin, ethene-(methyl) acrylic copolymer, ethene-(methyl) acrylate is (random, alternately) multipolymer, ethylene-butene copolymer, ethylene-hexene co-polymers, urethane, polyethylene terephthalate, the polyester such as PEN, polycarbonate, polyimide, polyether-ether-ketone, polyimide, polyetherimide, polymeric amide, fully aromatic polyamide, polyphenylene sulfide, aramid fiber (paper), glass, woven fiber glass, fluoro-resin, polyvinyl chloride, polyvinylidene dichloride, cellulose-based resin, silicone resin, metal (paper tinsel), paper etc.
In addition, as the material of base material 1, the polymkeric substance such as the crosslinked of aforementioned resin can be listed.Foregoing plastics film does not use with can stretching, and can use the film of the stretch processing implementing single shaft or twin shaft as required yet.Utilize the resin sheet being given heat-shrinkable by stretch processing etc., by making this base material 1 thermal contraction after dicing, binder layer 2 and the bond area of die bonding film 3 can be reduced, realize the facilitation of the recovery of semi-conductor chip.
The surface of base material 1 can implement usual surface treatment in order to improve with the adaptation of adjoining course, retentivity etc., the chemistry such as such as chromic acid process, ozone exposure, fire exposure, high-voltage electric shock exposure, ionizing radiation process or physical treatment, utilize the coating process of silane coupling agent (such as, aftermentioned adhesive substance).Aforementioned substrates 1 can suitably be selected material of the same race or not of the same race to use, and also can use blended multiple material as required.
The thickness of base material 1 is not particularly limited, can suitably determines, be generally about 5 ~ 200 μm.
As the tackiness agent of the formation for binder layer 2, be not particularly limited, such as, can use the common pressure-sensitive adhesive such as acrylic adhesives, elastomeric adhesive.As aforementioned pressure-sensitive adhesive, the aspect utilizing the clean cleaning of the organic solvent such as ultrapure water, alcohol etc. of electronic unit polluted is afraid of, preferably the acrylic adhesives of polymkeric substance based on acrylic polymers from semiconductor crystal wafer, glass etc.
As foregoing acrylic polymkeric substance, include, for example and send as an envoy in order to (methyl) alkyl acrylate (such as, methyl esters, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, secondary butyl ester, the tert-butyl ester, pentyl ester, isopentyl ester, own ester, heptyl ester, monooctyl ester, 2-ethylhexyl, different monooctyl ester, the ninth of the ten Heavenly Stems ester, the last of the ten Heavenly stems ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, cetyl ester, stearyl, the carbon number 1 ~ 30 of the alkyl such as eicosyl ester, the particularly straight-chain of carbon number 4 ~ 18 or the alkyl ester etc. of branched) and (methyl) acrylate base ester is (such as, ring pentyl ester, cyclohexyl etc.) in the one kind or two or more acrylic polymers etc. as monomer component.It should be noted that, (methyl) acrylate refers to acrylate and/or methacrylic ester, and (methyl) of the present invention is the same meaning.
Foregoing acrylic polymkeric substance also can comprise in order to the modification of force of cohesion, thermotolerance etc. as required can with the unit corresponding to other monomer component of aforementioned (methyl) alkyl acrylate or cycloalkyl ester copolymerization.As this monomer component, include, for example out the carboxyl group-containing monomers such as vinylformic acid, methacrylic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid; The anhydride monomers such as maleic anhydride, itaconic anhydride; The hydroxyl monomers such as (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-4-hydroxy butyl ester, the own ester of (methyl) vinylformic acid-6-hydroxyl, (methyl) vinylformic acid-8-hydroxyl monooctyl ester, (methyl) vinylformic acid-10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid-12-hydroxylauric ester, (methyl) vinylformic acid (4-hydroxymethylcyclohexyl) methyl esters; Styrene sulfonic acid, allyl sulphonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic, (methyl) acrylamide propane sulfonic acid, (methyl) sulfopropyl acrylate, (methyl) propane sulfonic acid etc. are containing sulfonic group monomer; The phosphorous acid-based monomers such as 2-hydroxylethyl acyl phosphate; Acrylamide, vinyl cyanide etc.These can the monomer component of copolymerization can use one kind or two or more.These can copolymerization monomer consumption be preferably whole monomer component less than 40 % by weight.
And then foregoing acrylic polymkeric substance also can comprise multi-functional monomer etc. as comonomer composition to carry out crosslinked as required.As this multi-functional monomer, include, for example out 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 multi-functional monomers also can use one kind or two or more.From the aspect of adhesion characteristic etc., the consumption of multi-functional monomer is preferably less than 30 % by weight of whole monomer component.
Foregoing acrylic polymkeric substance can obtain by single monomer or monomer mixture of more than two kinds being committed to polymerization.Polymerization also can be undertaken by the any-mode in solution polymerization, letex polymerization, mass polymerization, suspension polymerization etc.From the aspect of the pollution of the adherend prevented cleaning etc., the content of preferred low molecular weight substance is little.Set out from the side, the number-average molecular weight of acrylic polymers be preferably more than 100,000, more preferably 200,000 ~ about 3,000,000, be particularly preferably 300,000 ~ about 1,000,000.
In addition, also suitably external crosslinker can be adopted in order to the number-average molecular weight of the acrylic polymers of polymkeric substance based on improving etc. in aforementioned adhesion agent.As the concrete means of outside cross-linking method, so-called linking agents such as adding polyisocyanate compound, epoxy compounds, aziridine cpd, melamine series linking agent can be listed and the method making it react.When using external crosslinker, its consumption is according to the balance with the base polymer that will be cross-linked and then suitably determine according to the use as tackiness agent.Usually, relative to 100 weight part aforementioned base polymkeric substance, preferably following about compounding 5 weight parts, preferred compounding 0.1 ~ 5 weight part further.And then, the additives such as existing known various tackifier, anti-aging agent can also be added as required in tackiness agent except aforesaid ingredients.
Binder layer 2 can be formed by radiation-curing type tackiness agent.Radiation-curing type tackiness agent increases degree of crosslinking by the irradiation of the radioactive rays such as ultraviolet, can easily reduce its bounding force, by attaching the corresponding part 2a of part with workpiece and carry out radiation exposure only to the binder layer 2 shown in Fig. 2, the difference with the bounding force of other parts 2b can be set.
In addition, by correspondingly making the binder layer 2 of radiation-curing type solidify with the die bonding film 3 ' shown in Fig. 2, the preceding sections 2a that bounding force significantly reduces can easily be formed.Owing in solidification the preceding sections 2a that reduces of bounding force attaching die bonding film 3 ', therefore the preceding sections 2a of binder layer 2 and the interface of die bonding film 3 ' have the character easily peeled off when picking up.On the other hand, the part of not irradiating radioactive rays has sufficient bounding force, forms preceding sections 2b.In addition, also can after dicing and carry out before pickup to the irradiation of the radioactive rays of binder layer.
As previously mentioned, in the binder layer 2 of the die bonding film 10 of band cutting blade shown in Figure 1, the preceding sections 2b formed by uncured radiation-curing type tackiness agent and die bonding film 3 bond, and can guarantee confining force when cutting.So, radiation-curing type tackiness agent can make bonding/stripping balance the die bonding film 3 supported well for shaped like chips workpiece (semi-conductor chip etc.) being fixed on the adherends such as substrate.In the binder layer 2 of the die bonding film 11 of the band cutting blade shown in Fig. 2, preceding sections 2b can fix wafer central.
Radiation-curing type tackiness agent can use the functional group with radiation-curables such as carbon-carbon double bonds without particular limitation and show fusible material.As radiation-curing type tackiness agent, such as, can exemplify the radiation-curing type tackiness agent of the monomer component of compounding radiation-curable, the addition type of oligopolymer composition in the common pressure-sensitive adhesives such as foregoing acrylic tackiness agent, elastomeric adhesive.
As the monomer component of compounding radiation-curable, include, for example out oligourethane, carbamate (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylol methane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol monohydroxy five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, BDO two (methyl) acrylate etc.In addition, the oligopolymer composition of radiation-curable can list the various oligopolymer such as polyurethane series, polyethers system, Polyester, polycarbonate-based, polyhutadiene system, its molecular weight be about 100 ~ 30000 scope be suitable.About the monomer component of radiation-curable, the compounding amount of oligopolymer composition, the amount of the bounding force that can reduce binder layer suitably can be determined according to the kind of aforementioned adhesion oxidant layer.Usually, relative to base polymer 100 weight part such as acrylic polymers forming tackiness agent, be such as 5 ~ 500 weight parts, be preferably 40 ~ 150 weight parts about.
In addition, as radiation-curing type tackiness agent, except the radiation-curing type tackiness agent of the addition type of aforementioned explanation, also can list be used in polymer lateral chain or main chain or based on material that main chain terminal has a carbon-carbon double bond polymkeric substance, the radiation-curing type tackiness agent of inherent type.The radiation-curing type tackiness agent of inherent type does not need containing the oligopolymer composition etc. as low molecular composition, or do not contain under most cases, therefore, oligopolymer composition etc. can not through time ground move within the adhesive layer, the binder layer of stable Rotating fields can be formed, so preferably.
The aforementioned base polymer with carbon-carbon double bond can use without particular limitation to be had carbon-carbon double bond and has fusible material.As this base polymer, preferably using acrylic polymers as basic framework.As the basic framework of acrylic polymers, aforementioned illustrative acrylic polymers can be listed.
The method importing carbon-carbon double bond in subtend foregoing acrylic polymkeric substance is not particularly limited, and can adopt various method, and the method that carbon-carbon double bond imports to polymer lateral chain is easy in molecular designing.Such as, can listing: after making acrylic polymers and the monomer copolymerization with functional group in advance, the method for condensation or addition reaction can be carried out with the compound of the functional group of this functional group reactions and carbon-carbon double bond under the state of radiation-curable maintaining carbon-carbon double bond by having.
As the example of the combination of these functional groups, carboxyl and epoxy group(ing), carboxyl and '-aziridino, hydroxyl and isocyanate group etc. can be listed.In the middle of the combination of these functional groups, from the easy degree of reactive tracing, the combination of hydroxyl and isocyanate group is suitable.In addition, as long as the combination by these functional groups generates the aforementioned combination with the acrylic polymers of carbon-carbon double bond, the then any side of functional group in acrylic polymers and aforesaid compound, in the middle of aforementioned preferred combination, acrylic polymers has hydroxyl and the situation that aforesaid compound has isocyanate group is suitable.Now, as the isocyanate compound with carbon-carbon double bond, include, for example out methacryloyl isocyanate, 2-methacryloxyethyl isocyanic ester, a pseudoallyl-alpha, alpha-dimethylbenzyl isocyanic ester etc.In addition, as acrylic polymers, can use the material of the copolymerization such as the ether based compound of aforementioned illustrative hydroxyl monomer, 2-hydroxyethyl vinylethers, 4-hydroxy butyl vinyl ether, diethylene glycol monovinyl base ether.
The radiation-curing type tackiness agent of aforementioned inherent type can be used alone the aforementioned base polymer (particularly acrylic polymers) with carbon-carbon double bond, also can under the degree not making characteristic degradation monomer component, the oligopolymer composition of compounding aforementioned radiation-curable.The oligopolymer compositions of radiation-curable etc. are generally in the scope of 30 weight parts relative to 100 parts by weight of base polymkeric substance, are preferably the scope of 0 ~ 10 weight part.
When utilizing ultraviolet etc. to be cured, containing Photoepolymerizationinitiater initiater in aforementioned radiation-curing type tackiness agent.As Photoepolymerizationinitiater initiater, include, for example out the α-one alcohol based compounds such as 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone, Alpha-hydroxy-α, α '-dimethyl acetophenone, 2-methyl-2-hydroxypropiophenonepreparation, 1-hydroxy cyclohexyl phenylketone; The methyl phenyl ketone based compounds such as methoxyacetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenones, 2-methyl isophthalic acid-[4-(methylthio group)-phenyl]-2-morpholino propane-1-ketone; The benzoin ether based compounds such as ethoxybenzoin, benzoin iso-propylether, anisoin methyl ether; The ketal based compounds such as benzyl dimethyl ketal; The aromatic sulfonyl based compounds such as 2-naphthalic sulfonic chloride; The photolytic activity oxime compounds such as 1-benzophenone-1,1-propanedione-2-(O-ethoxy carbonyl) oxime; Benzophenone, benzoyl phenylformic acid, 3, the benzophenone based compounds such as 3 '-dimethyl-4-methoxy benzophenone; The thioxanthone based compounds such as thioxanthone, CTX, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-bis-clopenthixal ketones, 2,4-diethyl thioxanthones, 2,4-diisopropylthioxanthone; Camphorquinone; Halogenation ketone; Acylphosphine oxide; Acyl phosphonate etc.About the compounding amount of Photoepolymerizationinitiater initiater is such as 0.05 ~ 20 weight part relative to base polymer 100 weight part such as acrylic polymers forming tackiness agent.
In addition, as radiation-curing type tackiness agent, include, for example out disclosed in Japanese Laid-Open Patent Publication 60-196956 publication, containing the elastomeric adhesive, acrylic adhesives etc. with Photoepolymerizationinitiater initiaters such as photopolymerizable compound and carbonyl compound, organosulfur compound, superoxide, amine, salt based compound such as the polyaddition compound of more than 2 unsaturated link(age)s, the organoalkoxysilanes with epoxy group(ing).
Also can as required containing the compound utilizing radiation exposure painted in the binder layer 2 of aforementioned radiation-curing type.By making containing the compound utilizing radiation exposure painted in binder layer 2, can only make to have carried out the colored parts of radiation exposure.That is, the part 2a attaching part 3a corresponding with workpiece shown in Fig. 1 can be made painted.Therefore, can directly distinguish whether radioactive rays have been irradiated to binder layer 2 by visual, easily identify that workpiece attaches part 3a, easily carry out the laminating of workpiece.In addition, when utilizing optical sensor etc. to detect semi-conductor chip, its accuracy of detection improves, and can not make a mistake when the pickup of semi-conductor chip operation.
The compound utilizing radiation exposure painted be before radiation exposure for colourless or light, become coloured compound by radiation exposure.As the preferred concrete example of above-claimed cpd, leuco dye (leuco dye) can be listed.As leuco dye, preferably use usual triphenyl methane system, fluorane (fluoran) is, thiodiphenylamine system, auramine (auramine) are, the dyestuff of spiro-pyrans system.Specifically, 3-[N-(p-methylphenyl is amino)]-7-anilino fluorane, 3-[N-(p-methylphenyl)-N-methylamino]-7-anilino fluorane, 3-[N-(p-methylphenyl)-N-ethylamino]-7-anilino fluorane, 3-diethylamino-6-methyl-7-anilino fluorane, crystal violet lactone, 4 can be listed, 4 '; 4 "-three (dimethylamino) triphenylcarbinol, 4,4 ', 4 "-three (dimethylamino) triphenyl methane etc.
As the preferred developer used together with these leuco dyes, the electron acceptor(EA)s such as the initial polymer of all the time used resol, aromatic derivant carboxylate, atlapulgite can be listed, and then, when making tonal variation, also can combinationally use various known chromogenic reagent.
This compound utilizing radiation exposure painted can be included in radiation-curing type caking agent after being temporarily dissolved in organic solvent etc., also can make micronized and comprise in the adhesive in addition.It is desirable that the usage rate of this compound is less than 10 % by weight, is preferably 0.01 ~ 10 % by weight, more preferably 0.5 ~ 5 % by weight in binder layer 2.When the ratio of this compound is more than 10 % by weight, exceedingly absorbed by this compound the radioactive rays that binder layer 2 irradiates, therefore the solidification of the preceding sections 2a of binder layer 2 becomes insufficient, and bounding force does not fully reduce sometimes.On the other hand, in order to fully painted, preferably the ratio of this compound is set to more than 0.01 % by weight.
When utilizing radiation-curing type tackiness agent to form binder layer 2, also can carry out radiation exposure to a part for binder layer 2, make: the bounding force of the bounding force < other parts 2b of the preceding sections 2a of binder layer 2.
As the method forming preceding sections 2a in aforementioned adhesion oxidant layer 2, can list: form the binder layer 2 of radiation-curing type on support base material 1 after, the method that radioactive rays make it solidify is irradiated partly to preceding sections 2a.The radiation exposure of local can carry out across being formed the photomask attaching the corresponding pattern such as part 3b beyond part 3a with workpiece.In addition, the method etc. that point-like ground irradiation ultraviolet radiation makes it solidify can be listed.The formation of the binder layer 2 of radiation-curing type can be undertaken by being transferred on support base material 1 by the binder layer be arranged on barrier film.The radiation-curing of local also can carry out the binder layer 2 of the radiation-curing type arranged on barrier film.
In addition, when utilizing radiation-curing type tackiness agent to form binder layer 2, use by least one side of support base material 1, to attach part beyond the corresponding part of part 3a with workpiece all or part of carried out the base material of shading, after forming the binder layer 2 of radiation-curing type thereon, carry out radiation exposure, make to attach with workpiece corresponding partially cured of part 3a, the preceding sections 2a reducing bounding force can be formed.As light screening material, can be carried out in support film by the material that can form photomask printing, evaporation etc. and making.According to above-mentioned manufacture method, efficiency the die bonding film 10 of band cutting blade of the present invention can be manufactured well.
It should be noted that, the solidification occurring when radiation exposure to be caused by oxygen suppresses, it is desirable that pass through someway from the surperficial starvation (air) of the binder layer 2 of radiation-curing type.Such as, can list: cover the method on the surface of aforementioned adhesion oxidant layer 2 with barrier film, in nitrogen atmosphere, carry out the method etc. of the irradiation of the radioactive rays such as ultraviolet.
The thickness of binder layer 2 is not particularly limited, from the aspect such as the property taken into account of fixing maintenance preventing the defect of chip cut surface, adhesive linkage, is preferably about 1 ~ 50 μm.Be preferably 2 ~ 30 μm, more preferably 5 ~ 25 μm.
(manufacture method of the die bonding film of band cutting blade)
Die bonding film 10 with cutting blade such as makes as follows.
First, base material 1 can carry out masking by existing known film-forming method.As this film-forming method, such as, can exemplify the inflation extrusion molding, T mould extrusion molding, coetrusion, dry lamination method etc. in calendering masking method, casting method in organic solvent, enclosed system.
Then, coating adhesive composition solution on base material 1 and after forming coated film, by this coated film under prescribed conditions dry (carrying out heat cross-linking as required), forms binder layer 2.As coating process, be not particularly limited, include, for example out roll coating, screen-printing deposition, rotogravure application etc.In addition, as drying conditions, such as, carry out in drying temperature 80 ~ 150 DEG C, the scope of 0.5 ~ 5 minute time of drying.In addition, also can on barrier film coating adhesive composition and after forming coated film, under aforementioned drying condition, coated film is dry, form binder layer 2.Then, binder layer 2 is fitted on base material 1 together with barrier film.Thus, cutting blade 11 is made.
Die bonding film 3 such as makes as follows.
First, formation material and the resin composition solution of die bonding film 3 is made.Aforementioned resin solution can obtain as follows: suitably put in container by cationic for seizure additive, thermosetting resin, thermoplastic resin, filler etc. as required, be dissolved in organic solvent, stirs and makes it even, thus obtain.
As aforementioned organic solvents, if can make the uniform composition of formation die bonding film 3 dissolve, mixing or dispersion be just not particularly limited, existing known solvent can be used.As this solvent, include, for example out ketone series solvent, toluene, the dimethylbenzene etc. such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, acetone, methylethylketone, pimelinketone.Fast from rate of drying, can to obtain at an easy rate aspect, preferably uses methylethylketone, pimelinketone etc.
Then, resin composition solution is applied on base material barrier film after forming coated film with specific thickness, this coated film is dry under prescribed conditions, form bond layer (die bonding film 3).As coating process, be not particularly limited, include, for example out roll coating, screen-printing deposition, rotogravure application etc.In addition, as drying conditions, such as, carry out in drying temperature 70 ~ 160 DEG C, the scope of 1 ~ 5 minute time of drying.In addition, also can on barrier film coating resin composition solution and after forming coated film, under aforementioned drying condition, coated film is dry and form die bonding film 3.Then, die bonding film 3 is fitted on base material barrier film together with barrier film.
Then, autotomy respectively pitch cutting 11 and die bonding film 3 peel off barrier film, and both fit by the mode becoming binding face with die bonding film 3 and binder layer 2.Laminating such as can be undertaken by crimping.Now, laminating temperature is not particularly limited, such as, is preferably 30 ~ 50 DEG C, is more preferably 35 ~ 45 DEG C.In addition, line pressure is not particularly limited, such as, is 0.1 ~ 20kgf/cm, is more preferably 1 ~ 10kgf/cm.Then, peel off the base material barrier film on die bonding film 3, obtain the die bonding film 10 of the band cutting blade of present embodiment.
(manufacture method of semiconductor device)
The manufacture method of the semiconductor device of present embodiment comprises:
Prepare the operation of aforementioned thermosetting die bonding film; And
Clip aforementioned thermosetting die bonding film, by semi-conductor chip chip join to the chip join operation (hereinafter also referred to the 1st embodiment) on adherend.
In addition, the manufacture method of the semiconductor device of present embodiment also can comprise:
Prepare the operation of the die bonding film of aforementioned described band cutting blade;
The back side of the thermosetting die bonding film of the die bonding film of aforementioned strip cutting blade and semiconductor crystal wafer is carried out the bonding process of fitting;
Aforesaid semiconductor wafer is cut together with aforementioned thermosetting die bonding film, forms the cutting action of the semi-conductor chip of shaped like chips;
By former semiconductor chip together with aforementioned thermosetting die bonding film from the pickup process that the die bonding film of aforementioned strip cutting blade picks up; And
Clip aforementioned thermosetting die bonding film, by former semiconductor chip chip join to the chip join operation (hereinafter also referred to the 2nd embodiment) on adherend.
About the manufacture method of the semiconductor device of the first embodiment, manufacture method except the semiconductor device of the second embodiment employs the band die bonding film of cutting blade and the manufacture method of the semiconductor device of the first embodiment has been used alone except die bonding film this point difference, and other side is common.In the manufacture method of the semiconductor device of the 1st embodiment, as long as die bonding film is laggard is about to the operation that itself and cutting blade fit preparing, just can operate equally with the manufacture method of the semiconductor device of the 2nd embodiment thereafter.So the manufacture method below for the semiconductor device of the 2nd embodiment is described.
In the manufacture method of the semiconductor device of present embodiment, first, the die bonding film (preparatory process) of band cutting blade is prepared.About the die bonding film 10 of band cutting blade, peel off the barrier film be arranged at arbitrarily on die bonding film 3 aptly, use as follows.Below, limit is described for the situation of the die bonding film 10 using band cutting blade with reference to Fig. 3 limit.
First, the semiconductor crystal wafer of the die bonding film 3 in the die bonding film 10 of band cutting blade attaches on part 3a and crimps semiconductor crystal wafer 4, its bonding maintenance is fixed (bonding process).This operation limit is undertaken being undertaken by flanging by pressing means such as crimping rollers.Attaching temperature time fixing is not particularly limited, such as, is preferably in the scope of 40 ~ 90 DEG C.
Then, the cutting (cutting action) of semiconductor crystal wafer 4 is carried out.Thus, semiconductor crystal wafer 4 is cut to the size of regulation and singualtion, manufactures semi-conductor chip 5.The method of cutting is not particularly limited, such as, can carries out according to well-established law from the circuit face side of semiconductor crystal wafer 4.In addition, such as can adopt in this operation carry out cutting till the die bonding film 10 with cutting blade, be called as the cut-out mode etc. of entirely cutting (fullcut).As the cutting unit used in this operation, be not particularly limited, existing known device can be used.In addition, semiconductor crystal wafer is owing to being adhesively fixed by the die bonding film 10 of band cutting blade, therefore, it is possible to suppression chip defect, chip disperse, and can suppress the breakage of semiconductor crystal wafer 4.
Then, the pickup (pickup process) of semi-conductor chip 5 is carried out in order to peel off the semi-conductor chip of the die bonding film 10 being bonded and fixed to band cutting blade.As the method for pickup, be not particularly limited, existing known various method can be adopted.Such as, can list: carry die bonding film 10 side of cutting blade with pin by each semi-conductor chip 5 jack-up, and with pickup device pickup by the method etc. of the semi-conductor chip 5 of jack-up.
As pickup conditions, from the aspect preventing fragmentation, preferably the jack-up speed of pin is set to 5 ~ 100mm/ second, is more preferably set to 5 ~ 10mm/ second.
Herein, when binder layer 2 is ultraviolet hardening, picks up and carry out after to this binder layer 2 irradiation ultraviolet radiation.Thus, the bounding force of binder layer 2 pairs of die bonding films 3 reduces, and the stripping of semi-conductor chip 5 becomes easy.Its result, can pick up semi-conductor chip 5 with no damage.The conditions such as exposure intensity during uviolizing, irradiation time are not particularly limited, suitably set as required.In addition, as the light source that uviolizing uses, said light source can be used.It should be noted that, to binder layer carry out in advance uviolizing make it solidify and the binder layer of this solidification and die bonding film fitted time, uviolizing is herein unwanted.
Then, the semi-conductor chip 5 of pickup is clipped die bonding film 3 and be adhesively fixed (chip join operation) on adherend 6.As adherend 6, the semi-conductor chip etc. that can list lead frame, TAB film, substrate or make separately.Adherend 6 can be such as the deformation type adherend of easily distortion, also can for being difficult to the non-deformed type adherend (semiconductor crystal wafer etc.) be out of shape.
As aforesaid base plate, existing known substrate can be used.In addition, as aforementioned lead frame, the organic substrate die-attach area such as Cu lead frame, 42Alloy lead frame can be used, being made up of glass epoxy resin (glass-epoxy), BT (bismaleimide-triazine), polyimide etc.But the present invention is not limited to this, also comprises and semi-conductor chip can be fixed, be electrically connected with semi-conductor chip and the circuit substrate used.
Then, because die bonding film 3 is heat curing-type, therefore by thermofixation, semi-conductor chip 5 is adhesively fixed on adherend 6, improves high-temperature capability (heat curing processes).Can carry out at Heating temperature 80 ~ 200 DEG C, be preferably 100 ~ 175 DEG C, be more preferably 100 ~ 140 DEG C.In addition, can be 0.1 ~ 24 littlely to carry out at present in heat-up time, be preferably 0.1 ~ 3 hour, be more preferably 0.2 ~ 1 hour.In addition, thermofixation also can be carried out under an increased pressure.As pressurized conditions, be preferably 1 ~ 20kg/cm 2scope in, be more preferably 3 ~ 15kg/cm 2scope in.The thermofixation adding pressure such as can be carried out in the chamber being filled with non-active gas.It should be noted that, clip die bonding film 3 and semi-conductor chip 5 is bonded and fixed to substrate etc. and the product obtained can be used in Reflow Soldering operation.
The shear bond power of the die bonding film 3 after thermofixation, relative to adherend 6, is preferably more than 0.2MPa, is more preferably 0.2 ~ 10MPa.When the shear bond power of die bonding film 3 is at least more than 0.2MPa, during wire-bonded operation, can not because of the ultrasonic vibration in this operation, heating and produce shearing strain at die bonding film 3 and the bonding plane of semi-conductor chip 5 or adherend 6.That is, semi-conductor chip can not move because of ultrasonic vibration during wire-bonded, prevents the success ratio of wire-bonded from reducing thus.
Then, as required, as shown in Figure 3, with bonding wire 7, the front end of the portion of terminal (inner lead) of adherend 6 is carried out being electrically connected (wire-bonded operation) with the electrode pad (not shown) on semi-conductor chip 5.As aforementioned bonding wire 7, such as, can use gold thread, aluminum steel or copper cash etc.About temperature when carrying out wire-bonded, can carry out in the scope of 80 ~ 250 DEG C, preferably 80 ~ 220 DEG C.In addition, this heat-up time be several seconds ~ carry out under several minutes.Line carries out based on hyperacoustic vibrational energy with based on the crimping energy applying pressurization by combinationally using under being connected to the state be heated to be in foregoing temperature range.This operation can not be carried out the thermofixation of die bonding film 3 and implement.In addition, in the process of this operation, with die bonding film 3, semi-conductor chip 5 and adherend 6 are not fixed.
Then, as required, as shown in Figure 3, potting resin 8 packaged semiconductor 5 (packaging process) is utilized.This operation is in order to protect the semi-conductor chip 5, the bonding wire 7 and carrying out that are equipped on adherend 6.This operation can by carrying out with the resin forming of mould by encapsulation.As potting resin 8, such as, use the resin of epoxy.About Heating temperature during resin package, usually at 175 DEG C, carry out 60 ~ 90 seconds, but the present invention is not limited to this, such as, can solidifies several minutes at 165 ~ 185 DEG C.Thus, make potting resin solidify and clip die bonding film 3 semi-conductor chip 5 is fixed with adherend 6.That is, in the present invention, even if when not carrying out aftermentioned after fixing operation, die bonding film 3 also can be utilized in this operation to be fixed, the shortening of the minimizing of worker ordinal number and the manufacturing time of semiconductor device can be contributed to.In addition, this packaging process also can adopt the method (such as, see Japanese Unexamined Patent Publication 2013-7028 publication) embedding semi-conductor chip 5 in the encapsulation sheet of sheet.
Then, heat as required, make in aforementioned encapsulation operation, to solidify not enough potting resin 8 and solidify (after fixing operation) completely.Even if when packaging process chips bonding film 3 not completely thermofixation, also can complete thermofixation together with potting resin 8 at this operation chips bonding film 3.Heating temperature in this operation is different according to the kind of potting resin, such as, be that in the scope of 165 ~ 185 DEG C, heat-up time is 0.5 ~ 8 hours.
Thus, the semiconductor device shown in Fig. 3 is obtained.Even if the semiconductor device of manufacture like this is more than 1 also have the die bonding film 3 of sufficient ion-catching through thermal history owing to having aforementioned than B/A, therefore, it is possible to suppress with positively charged ion to be the malfunction of reason.
It should be noted that, the manufacture method of the semiconductor device of present embodiment also can be carried out as follows: chip join operation temporarily fixing after carry out wire-bonded and without the heat curing processes based on heat treated of die bonding film 3, and then by potting resin packaged semiconductor 5, by this potting resin solidification (after fixing).Now, shear bond power during die bonding film 3 temporarily fixing, relative to adherend 6, is preferably more than 0.2MPa, is more preferably 0.2 ~ 10MPa.When shear bond power during die bonding film 3 temporarily fixing is at least more than 0.2MPa, even if carry out wire-bonded operation without heating process, also can not because of the ultrasonic vibration in this operation, heating and produce shearing strain at die bonding film 3 and the bonding plane of semi-conductor chip 5 or adherend 6.That is, semi-conductor chip can not move because of ultrasonic vibration during wire-bonded, prevents the success ratio of wire-bonded from reducing thus.It should be noted that, temporarily fixedly refer to following state: make this die bonding film solidify (formation semi-cured state), by state fixing for semi-conductor chip 5 with the mode that can not impact in operation afterwards, the degree of state of carrying out completely with the curing reaction not reaching thermosetting die bonding film.It should be noted that, when carrying out wire-bonded and without the heat curing processes of the heat treated based on die bonding film, the operation of above-mentioned after fixing is equivalent to the heat curing processes in this specification sheets.
It should be noted that, the die bonding film of band cutting blade of the present invention also can be suitably used for stacked for multiple semi-conductor chip and carry out three-dimensional situation of installing.Now, can between semi-conductor chip stacked die bonding film and spacer, also can only stacked die bonding film and not stacked spacer between semi-conductor chip, suitably can change according to manufacturing condition, purposes etc.
In above-mentioned embodiment, the situation being die bonding film for semiconductor device resin film of the present invention is illustrated.But, as long as the film used in semiconductor device resin film semiconductor device of the present invention is just not limited to this example, also can be the flip chip type semiconductor back surface film for the formation of the back side of having carried out the semiconductor element that flip-chip connects on adherend, also can be the packaging film for packaging semiconductor.
Embodiment
Below, the suitable embodiment of this invention is described illustratively in detail.But the material recorded in this embodiment, compounding amount etc. as long as no the record of being particularly limited to property, are then not that the main idea of this invention is only defined in these examples.
The composition used in embodiment is described.
Acrylic copolymer: the TEISAN RESINSG-P3 (weight-average molecular weight: 850,000, second-order transition temperature: 12 DEG C) that Nagase ChemteX Corporation manufactures
Resol: the bright MEH-7851SS (there is the resol of biphenyl aralkyl skeleton, softening temperature 67 DEG C, hydroxyl equivalent 203g/eq.) with changing into Co., Ltd.'s manufacture
Epoxy resin: the YDCN-700-2 (o-cresol phenolic epoxy varnish, epoxy equivalent (weight) 200, softening temperature 61 DEG C) that Nippon Steel Chemical Co., Ltd manufactures
Mineral filler: the SO-E2 (melting spherical silicon dioxide, median size 0.5 μm) that Admatechs Co., Ltd. manufactures
Catch cationic additive: the IXEPLAS-A1 (the three compositions system hydrous oxide of magnesium, aluminium and zirconium, median size 0.5 μm) that Toagosei Co., Ltd manufactures
Catch cationic additive: the BT-120 (1,2,3-benzotriazole) that Johoku Chemical Co., Ltd. manufactures
Catch cationic additive: the IXE-100 (zirconium system hydrous oxide, median size 1.0 μm) that Toagosei Co., Ltd manufactures
It should be noted that, carry out surface treatment in advance as IXEPLAS-A1 and IXE-100 catching cationic additive.Surface treatment is undertaken by dry method, processes with the silane coupling agent of the amount (silane coupling agent treatment capacity) shown in table 1.Silane coupling agent uses the KBM503 (3-methacryloxypropyl) of SHIN-ETSU HANTOTAI's chemistry.In addition, when being used as the BT-120 catching cationic additive, silane coupling agent is dissolved in organic solvent together with other composition.
[embodiment and comparative example]
According to the compounding ratio recorded in table 1, using each component dissolves, be scattered in methylethylketone as organic solvent, obtain the resin composition solution of concentration 20 % by weight.This resin composition solution is applied to carried out silicone release process, thickness be on the demoulding process film formed by pet film of 38 μm after, at 110 DEG C dry 5 minutes.Thus, the resin film of thickness 25 μm is obtained.
(calculating than B/A)
The cupric ion catch rate A of the resin film 1. before thermofixation [calculate]
Each resin film (thickness 25 μm) is cut out 2.5g respectively, bent, put in columned closed Teflon (registered trademark) container of diameter 58mm, height 37mm, add copper (II) deionized water solution (CuCl of 10ppm 2the aqueous solution) 50ml.Then, place 20 hours at 120 DEG C in freeze-day with constant temperature machine (ESPEC Corp. manufacture, PV-231).Then, room temperature is cooled to.After taking out film, ICP-AES (manufacture of SII Nano-Technology Co., Ltd., SPS-1700HVR) is used to measure the concentration (copper ion concentration X) of the cupric ion in the aqueous solution.
Then, following formula (1) is utilized to calculate the cupric ion catch rate A of the resin film before thermofixation.Show the result in table 1.
Formula (1): [(10-X)/10] × 100 (%)
The cupric ion catch rate B of the resin film 2. after thermofixation [calculate]
The mode being 2.5g with the weight after making stripping demoulding process film cuts out each resin film (thickness 25 μm), after being bent, and thermofixation 5 hours at 175 DEG C.Then, peel off demoulding process film, put in columned closed Teflon (registered trademark) container of diameter 58mm, height 37mm, add copper (II) deionized water solution (CuCl of 10ppm 2the aqueous solution) 50ml.Then, place 20 hours at 120 DEG C in freeze-day with constant temperature machine (ESPEC Corp. manufacture, PV-231).Then, room temperature is cooled to.After taking out film, ICP-AES (manufacture of SII Nano-Technology Co., Ltd., SPS-1700HVR) is used to measure the concentration (copper ion concentration Y) of the cupric ion in the aqueous solution.
Then, following formula (2) is utilized to calculate the cupric ion catch rate B of the resin film after thermofixation.Show the result in table 1.
Formula (2): [(10-Y)/10] × 100 (%)
According to the cupric ion catch rate A calculated and cupric ion catch rate B, calculate and compare B/A.Show the result in table 1.
(mensuration of 5% weightless temperature)
Weigh 10mg sample, utilize differential thermal balance (TG-DTA (Rigaku Corporation manufactures)) to measure between 40 ~ 550 DEG C in air atmosphere, with heat-up rate 10 DEG C/min.Temperature when reading weightless 5%.
(pH of the aqueous solution after cupric ion seizure)
For the aqueous solution obtained time above-mentioned the cupric ion catch rate B of the resin film 2. after thermofixation " calculate " (measuring aqueous solution during copper ion concentration Y), Kasutani ACTpH Meter (D-51, Horiba Ltd manufacture) is used to measure.Show the result in table 1.
It should be noted that, the pH of 10ppm copper (II) deionized water solution before solvent impregnated resin film is 5.6.
Use the embodiment 1 of IXEPLASE-A1 and the pH of embodiment 2 to be between 4.5 ~ 5.5, also inhibits pH after utilizing ion-exchange to carry out the seizure of cupric ion becomes acid.Therefore, infer and also maintain higher ion-catching after thermofixation.
On the other hand, the pH using the comparative example 2 of IXE-100 is about 3.5, acid grow.Therefore, infer that the ion-catching after thermofixation reduces.
table 1

Claims (6)

1. a semiconductor device resin film, is characterized in that,
The semiconductor device resin film of the heavy 2.5g before heat of immersion in the aqueous solution 50ml with 10ppm cupric ion is solidified and at 120 DEG C the copper ion concentration (ppm) placed in the described aqueous solution after 20 hours be set to X,
And the semiconductor device resin film of the heavy 2.5g of thermofixation after 5 hours at 175 DEG C will be immersed in the aqueous solution 50ml with 10ppm cupric ion and at 120 DEG C, the copper ion concentration (ppm) placed in the described aqueous solution after 20 hours is set to Y time
The cupric ion catch rate A calculated by following formula (1) is more than 1 with the ratio B/A of the cupric ion catch rate B calculated by following formula (2),
Formula (1): [(10-X)/10] × 100 (%)
Formula (2): [(10-Y)/10] × 100 (%).
2. semiconductor device resin film according to claim 1, is characterized in that, 5% weightless temperature is more than 200 DEG C.
3. semiconductor device resin film according to claim 1, is characterized in that, containing catching cationic inorganic ion scavenger.
4. semiconductor device resin film according to claim 3, is characterized in that, the content of described inorganic ion scavenger is 1 ~ 30 % by weight.
5. semiconductor device resin film according to claim 3, it is characterized in that, in the aqueous solution 50ml of cupric ion with 10ppm, be immersed in the semiconductor device resin film of the weight 2.5g of thermofixation after 5 hours at 175 DEG C and the pH placing the described aqueous solution after 20 hours at 120 DEG C is in the scope of 4 ~ 6.
6. a manufacture method for semiconductor device, is characterized in that, comprises following operation:
Prepare the operation of the semiconductor device resin film according to any one of Claims 1 to 5; And
Clip described semiconductor device resin film, by semi-conductor chip chip join to the chip join operation on adherend.
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