CN101641766A - Adhesive film for semiconductor, composite sheet, and method for producing semiconductor chip using them - Google Patents

Adhesive film for semiconductor, composite sheet, and method for producing semiconductor chip using them Download PDF

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Publication number
CN101641766A
CN101641766A CN 200880009599 CN200880009599A CN101641766A CN 101641766 A CN101641766 A CN 101641766A CN 200880009599 CN200880009599 CN 200880009599 CN 200880009599 A CN200880009599 A CN 200880009599A CN 101641766 A CN101641766 A CN 101641766A
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semiconductor
semiconductor wafer
adhering film
semiconductor chip
dicing tape
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Chinese (zh)
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中村祐树
北胜勉
片山阳二
畠山惠一
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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    • 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
    • H01L2224/01—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
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/2919—Material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • H01L2224/29191—The principal constituent being an elastomer, e.g. silicones, isoprene, neoprene
    • 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
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/10251—Elemental semiconductors, i.e. Group IV
    • H01L2924/10253—Silicon [Si]

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Abstract

There is provided an adhesive film for a semiconductor, which can be attached to a semiconductor wafer at low temperature and which allows semiconductor chips to be obtained at high yield from the semiconductor wafer while sufficiently inhibiting generation of chip cracks and burrs. The adhesive film for a semiconductor comprises a polyimide resin that can be obtained by reaction between a tetracarboxylic dianhydride containing 4,4'-oxydiphthalic dianhydride represented by chemical formula (I) below and a diamine containing a siloxanediamine represented by the following general formula (II) below, and that can be attached to a semiconductor wafer at 100 DEG C or below.

Description

Adhesive film for semiconductor, composite sheet and use the manufacture method of their semiconductor chip
Technical field
The manufacture method that the present invention relates to adhesive film for semiconductor, composite sheet and used their semiconductor chip.
Background technology
When being installed on semiconductor chip on the support unit, tube core welding (die bonding) material as bonding semiconductor chip and support unit mainly used silver paste (silver paste) in the past.But, along with the miniaturisation high-performanceization of semiconductor chip and the miniaturization precise treatment of employed support unit, in using the method for silver paste, exist because the problem of generation of the not good situation during wire-bonded (wire bonding) that the inclination of the oozing out of paste, semiconductor chip causes and so on becomes obvious day by day.For this reason, replace silver paste gradually in recent years and use bonding film (adhesive film for semiconductor).
As using bonding film to obtain the mode of semiconductor device, there is monolithic to attach mode and chip back surface attaching mode.
In monolithic attaching mode, from the bonding film of reel, utilize cutting or punching to cut out monolithic, the monolithic of this bonding film is bonded in support unit.By the bonding film that is adhered on the support unit, with additionally utilize the cutting action singualtion semiconductor chip be bonded on support unit.As required through wire-bonded operation, sealing process etc. obtain semiconductor device thereafter.But, attach at monolithic under the situation of mode, owing to being used for that bonding film is cut out the apparatus for assembling that is adhered to the special use on the support unit with monolithic, therefore compare the problem that has manufacturing cost to uprise with the method for using silver paste.
In chip back surface attaching mode, at first, attach bonding film and dicing tape successively at the back side of semiconductor wafer.After this, with semiconductor wafer cutting and be divided into a plurality of semiconductor chips, and with bonding film along with each semiconductor chip cuts off., semiconductor chip with the bonding film that be laminated in its back side picked (pick-up), semiconductor chip is bonded on support unit by bonding film thereafter.Again through operation such as heating, curing, wire-bonded obtain semiconductor device thereafter.Attach at chip back surface under the situation of mode, do not need to be used for the apparatus for assembling with bonding film singualtion, can directly use existing silver paste apparatus for assembling, perhaps the part that will install by additional heat dish etc. improves and uses.Thus, in the middle of the method for having used bonding film, receive much concern as the method that can control manufacturing cost lower.
On the other hand, in recent years, as method with the semiconductor wafer cutting, following stealth cutting (stealth dicing) method was proposed: by optionally forming upgrading portion to the semiconductor wafer irradiating laser and in semiconductor wafer inside, and semiconductor wafer is cut off (patent documentation 1,2) along upgrading portion.In this method, for example, by the stretching dicing tape to the semiconductor wafer stress application, thereby along upgrading portion semiconductor wafer is divided into a plurality of semiconductor chips.
Patent documentation 1: TOHKEMY 2002-192370 communique
Patent documentation 2: TOHKEMY 2003-338467 communique
Attach at above-mentioned chip back surface under the situation of mode, in the cutting of semiconductor wafer, need bonding film is also side by side cut off.But, if utilize and to have used the common cutting method of diamond blade that semiconductor wafer and bonding film are side by side cut off, just have crack (chip crackle) in the semiconductor chip side after cut-out or in section bonding film form burr and produce the problem of a lot of burrs (burr).If there is this chip crackle or burr, then, cause product percent of pass to reduce picking in the semiconductor chip semiconductor chip fracture easily that becomes.
So, in order to suppress the generation of chip crackle or burr, the inventor etc. study following method, this method comprises: the operation of preparing laminated body, semiconductor wafer, adhesive film for semiconductor and dicing tape are stacked gradually, according to semiconductor wafer being divided into a plurality of semiconductor chips and at least a portion of the thickness direction of adhesive film for semiconductor not being cut off and residual mode, form grooving from semiconductor wafer side; By dicing tape is stretched along direction that a plurality of semiconductor chips are separated from each other, and the operation that adhesive film for semiconductor is cut apart along grooving.
Yet, when using adhesive film for semiconductor in the past and utilizing said method to cut, obviously have and be difficult to problem that adhesive film for semiconductor is fully disconnected along grooving.
In addition, expectation suppresses to be accompanied by chip crackle or the burr that cutting produces to a certain extent by above-mentioned stealthy cutting.But, under the situation that adopts the method for coming cutting semiconductor chip by laser processing at semiconductor wafer formation upgrading portion after-drawing dicing tape, only utilize the stretching of dicing tape to be difficult to adhesive film for semiconductor is fully disconnected, obviously, the semiconductor chip that hence one can see that obtains high qualification rate is actually difficulty.
In addition, use formed grooving laminated body method or utilize in the method for stealthy cutting, though by in bonding film, containing a large amount of fillers, bonding film ruptures easily, can suppress the generation of burr to a certain extent, yet have the problem that is difficult at low temperatures bonding film is attached to semiconductor wafer under this situation.For inhibition of the damage that realizes the thermal process by the warpage of semiconductor wafer or each parts is caused etc., preferably bonding film can be attached to semiconductor wafer under alap temperature.
Summary of the invention
The present invention finishes in view of aforesaid situation, its purpose is, a kind of adhesive film for semiconductor is provided, it can be attached to semiconductor wafer at low temperatures, and can in the generation that suppresses chip crackle or burr fully, obtain semiconductor chip by semiconductor wafer with good product percent of pass.In addition, the present invention also aims to, a kind of method is provided, it uses this adhesive film for semiconductor, can obtain semiconductor chip with good product percent of pass by semiconductor wafer in the generation that suppresses chip crackle or burr fully.
According to an aspect, the present invention relates to a kind of can be at the adhesive film for semiconductor that is attached to semiconductor wafer below 100 ℃.Adhesive film for semiconductor of the present invention contains polyimide resin, can utilize with the ratio more than the 50 overall quality % and contain by 4 of following chemical formula (I) expression, the tetracarboxylic dianhydride of the two phthalic anhydrides of 4 '-oxygen obtains with the reaction that contains the diamines of the siloxane diamine of being represented by following general formula (II) with the ratio more than the 30 overall quality %.In the formula (II), R represents that carbon number is that 1～5 alkyl, carbon number are 1～5 alkoxyl, phenyl or phenoxy group, can be identical or different with a plurality of R in a part, and n and m represent 1～3 integer respectively independently.
Figure G2008800095998D00031
The adhesive film for semiconductor of the invention described above just can be attached to semiconductor wafer at low temperatures by adopting above-mentioned specific polyimide resin, and is not also having disconnection fully under the situation of burr easily when being stretched.Consequently, use this adhesive film for semiconductor, in the generation that suppresses chip crackle or burr fully, obtain semiconductor chip by semiconductor wafer with good product percent of pass.
The vitrification point of above-mentioned polyimide resin is preferably more than 30 ℃ below 80 ℃.If vitrification point is in this scope, the operation that then is attached to semiconductor wafer at low temperatures will become easy especially, in addition, bonding film becomes the material that does not at room temperature have viscosity or have the viscosity of appropriateness, considers it also is favourable from the aspect of operability, the property disposed.
Adhesive film for semiconductor of the present invention also can contain Thermocurable composition and filler.Under this situation, the content of filler with respect to the quality optimization of this adhesive film for semiconductor less than 30 quality %.By controlling the content of filler lower to a certain extent, the operation that is attached to semiconductor wafer at low temperatures will become more easy, in addition, and the generation of crackle (the reflow crack) that can further suppress to reflux.
According on the other hand, the present invention relates to a kind of adhesive film for semiconductor with the invention described above, be laminated in the composite sheet of dicing tape of the one side side of this adhesive film for semiconductor.By using this composite sheet, can more effectively obtain semiconductor chip and semiconductor device with simple operation.
Aforesaid adhesive film for semiconductor of the present invention or composite sheet are applicable in the manufacture method of semiconductor chip of the present invention as follows.
The manufacture method of semiconductor chip of the present invention has: the operation of preparing duplexer, the adhesive film for semiconductor and the dicing tape of semiconductor wafer, the invention described above are stacked gradually, according to semiconductor wafer being divided into a plurality of semiconductor chips, and the mode of at least a portion of the thickness direction of adhesive film for semiconductor not cut off and keeping forms grooving from semiconductor wafer side; By dicing tape is stretched along direction that a plurality of semiconductor chips are separated from each other, and the operation that adhesive film for semiconductor is cut apart along grooving.
The manufacture method of semiconductor chip of the present invention also can have: the operation of preparing duplexer, the adhesive film for semiconductor and the dicing tape of semiconductor wafer, the invention described above are stacked gradually, utilize laser processing to form upgrading portion at semiconductor wafer along the line that semiconductor wafer is divided into a plurality of semiconductor chips; By dicing tape is stretched along direction that a plurality of semiconductor chips are separated from each other, and the operation that semiconductor wafer is divided into a plurality of semiconductor chips and adhesive film for semiconductor is partly cut along upgrading.
According to the manufacture method of the invention described above, can in the generation that suppresses chip crackle or burr fully, obtain semiconductor chip by semiconductor wafer with good product percent of pass.
According to the present invention, following adhesive film for semiconductor can be provided, it can be attached to semiconductor wafer at low temperatures, and in the generation that suppresses chip crackle or burr fully, obtains semiconductor chip with good product percent of pass by semiconductor wafer.In addition, adhesive film for semiconductor of the present invention is also very excellent aspect thermal endurance (high adhesiveness under the high temperature and the crackle of anti-backflow property etc.) and moisture-proof reliability.
Manufacturing method according to the invention can obtain semiconductor chip with good product percent of pass by semiconductor wafer in the generation that suppresses chip crackle or burr fully.In addition, manufacturing method according to the invention can also realize the raising of the process velocity of semiconductor device.
Description of drawings
Fig. 1 is the profile of manufacture method of the semiconductor chip of expression first execution mode.
Fig. 2 is the profile of manufacture method of the semiconductor chip of expression first execution mode.
Fig. 3 is the profile of manufacture method of the semiconductor chip of expression first execution mode.
Fig. 4 is the profile of manufacture method of the semiconductor chip of expression first execution mode.
Fig. 5 is the profile of manufacture method of the semiconductor chip of expression first execution mode.
Fig. 6 is the profile of manufacture method of the semiconductor chip of expression second execution mode.
Fig. 7 is the profile of manufacture method of the semiconductor chip of expression second execution mode.
Fig. 8 is the profile of manufacture method of the semiconductor chip of expression second execution mode.
Fig. 9 is the profile of manufacture method of the semiconductor chip of expression second execution mode.
Figure 10 is the profile of an execution mode of expression semiconductor device.
Figure 11 is the figure of stress-deformation curve of the tension test of expression adhesive film for semiconductor.
Figure 12 is the figure of stress-deformation curve of the tension test of expression adhesive film for semiconductor.
Figure 13 is the method for vitrification point is obtained in expression according to the relation of displacement and temperature figure.
Figure 14 is that expression is used to carry out the schematic diagram that chip peels the determinator of test.
Wherein, 1 ... semiconductor wafer, 1a ... upgrading portion, 2 ... adhesive film for semiconductor, 3 ... dicing tape, 4 ... cutting blade, 7 ... the base material that has wiring, 8 ... closing line, 9 ... sealing resin layer, 10,10a, 10b ... semiconductor chip, 20 ... laminated body, 40 ... grooving, 50 ... cut apart preset lines, 100 ... semiconductor device.
Embodiment
Below, preferred embodiment be elaborated to of the present invention.But the present invention is not limited to following execution mode.
Adhesive film for semiconductor
The adhesive film for semiconductor of present embodiment can be attached to semiconductor wafer below 100 ℃.Here, the adhesive film for semiconductor of the temperature that will remain regulation is attached to semiconductor wafer when pressurizeing as required after,, then is judged as and attaches if adhesive film for semiconductor is fixed with the degree of not peeling off naturally from semiconductor wafer.More particularly, for example the intensity that divests at the interface of adhesive film for semiconductor and semiconductor wafer is to get final product more than the 20N/m.Adhesive film for semiconductor for example can use the hot rolling laminator of the temperature that is set at below 100 ℃ to be attached to semiconductor wafer.The mensuration that divests intensity can be in 25 ℃ atmosphere, adopts 90 ° of stretching angles, draw speed 50mm/ minute to carry out.For example, can be by the content that reduces filler, the polyimide resin that use has low Tg (being preferably below 80 ℃), obtaining can be at the adhesive film for semiconductor that is attached to semiconductor wafer below 100 ℃.The temperature that adhesive film for semiconductor can be attached to semiconductor wafer is more preferably below 95 ℃, more preferably below 90 ℃.
The adhesive film for semiconductor of present embodiment contains the polyimide resin that has by the formation unit of following general formula (A) expression.Polyimide resin for example can utilize and comprise the reaction that utilizes tetracarboxylic dianhydride and diamines and generate the step of polyamic acid and obtained by the method that polyamic acid generates the step of polyimide resin.Under this situation, R in the formula (10) 1Be the residue of 4 valencys that derive from the tetracarboxylic dianhydride, R 2Residue for the divalence that derives from diamines.
Figure G2008800095998D00061
The tetracarboxylic dianhydride who uses in order to obtain polyimide resin comprises by 4 of following chemical formula (I) expression, two phthalic anhydride (following according to circumstances be called " ODPA " of 4 '-oxygen.)。In other words, polyimide resin contains the formation unit by following general formula (I-A) expression.R in the formula (I-A) 2R with formula (A) 2Synonym.
Figure G2008800095998D00071
50 quality % in preferred polyimide resin synthetic among the used tetracarboxylic dianhydride are above to be ODPA.If the ratio of ODPA, then has the moisture-proof of bonding film and the tendency that breaking property reduces easily less than 50 quality %.According to identical viewpoint, the ratio of ODPA is more preferably more than the 60 quality %, more preferably more than the 70 quality %.
The tetracarboxylic dianhydride both can only be contained ODPA, also can also contain ODPA compound in addition.As with the compound of ODPA and usefulness, for example can enumerate pyromellitic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 2, two (2,3-dicarboxyl phenyl) the propane dianhydrides of 2-, 1,1-two (2,3-dicarboxyl phenyl) ethane dianhydride, 1, two (3,4-dicarboxyl phenyl) the ethane dianhydrides of 1-, two (2,3-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, 3,4,9, the 10-perylenetetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, benzene-1,2,3, the 4-tetracarboxylic dianhydride, 3,4,3 ', 4 '-benzophenone tetracarboxylic dianhydride, 2,3,2 ', 3 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,2,4,5-naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 1,2-(ethylidene) two (trimellitic anhydrides), 1,3-(trimethylene) two (trimellitic anhydrides), 1,4-(tetramethylene) two (trimellitic anhydrides), 1,5-(pentamethylene) two (trimellitic anhydrides), 1,6-(hexa-methylene) two (trimellitic anhydrides), 1,7-(heptamethylene) two (trimellitic anhydrides), 1,8-(eight methylene) two (trimellitic anhydrides), 1,9-(nine methylene) two (trimellitic anhydrides), 1,10-(decamethylene) two (trimellitic anhydrides), 1,12-(ten dimethylenes) two (trimellitic anhydrides), 1,16-(ten hexa-methylenes) two (trimellitic anhydrides), 1,18-(18 methylene) two (trimellitic anhydrides), 2,6-dichloronaphtalene-1,4,5, the 8-tetracarboxylic dianhydride, 2,7-dichloronaphtalene-1,4,5, the 8-tetracarboxylic dianhydride, 2,3,6,7-Tetrachloronaphthalene-1,4,5, the 8-tetracarboxylic dianhydride, luxuriant and rich with fragrance-1,8,9, the 10-tetracarboxylic dianhydride, pyrazine-2,3,5, the 6-tetracarboxylic dianhydride, thiophene-2,3,4, the 5-tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) dimethylsilane dianhydride, two (3,4-dicarboxyl phenyl) aminomethyl phenyl silane dianhydride, two (3,4-dicarboxyl phenyl) diphenyl silane dianhydride, 1,4-two (3,4-dicarboxyl phenyl dimetylsilyl) benzene dianhydride, 1, two (3,4-dicarboxyl phenyl)-1 of 3-, 1,3,3-tetramethyl bicyclohexane dianhydride, TOPOT 2,2 (trimellitic anhydride), the ethene tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, decahydronaphthalenes-1,4,5, the 8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydro-naphthalenc-1,2,5, the 6-tetracarboxylic dianhydride, pentamethylene-1,2,3, the 4-tetracarboxylic dianhydride, pyrrolidines-2,3,4, the 5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, two (export-oriented-two ring [2.2.1] heptane-2,3-dicarboxylic anhydride) sulfone, dicyclo [2.2.2] suffering-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 2,2-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride, 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydrides of 2-, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 1, two (2-hydroxyl hexafluoro isopropyl) benzene of 4-two (trimellitic anhydride), 1, two (2-hydroxyl hexafluoro isopropyl) benzene of 3-two (trimellitic anhydride), 5-(2, the 5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride and oxolane-2,3,4, the 5-tetracarboxylic dianhydride.They both may be used alone, can also be used in combination multiple.
The diamines that uses in order to obtain polyimide resin comprises the siloxane diamine by following general formula (II) expression.In other words, polyimide resin contains the formation unit by following general formula (II-A) expression.R in the formula (II-A) 1, n and m and formula (A) R 1, n and m synonym.The polyimide resin of present embodiment often contains the formation unit by following general formula (10) expression.Any one of the formation unit of the formation unit of the formation unit of formula (10) and formula (I-A) and formula (II-A) is all suitable.
Figure G2008800095998D00091
In the above-mentioned formula, R represents that carbon number is that 1～5 alkyl, carbon number are 1～5 alkoxyl, phenyl or phenoxy group, can be identical or different with a plurality of R in a part, and n and m represent 1～3 integer respectively independently.It is 1～5 alkyl that R is preferably carbon number, and most typical is methyl.N and m are preferably 3.
As the concrete example of the siloxane diamine of formula (II), can enumerate 1,1,3,3-tetramethyl-1, two (2-amino-ethyl) disiloxane, 1 of 3-, 1,3,3-tetramethyl-1, two (3-aminopropyl) disiloxane, 1,1 of 3-, 3,3-tetraphenyl-1, two (2-amino-ethyl) disiloxane and 1,1 of 3-, 3,3-tetraphenyl-1, two (3-aminopropyl) disiloxane of 3-.
30 quality %～100 quality % in preferred polyimide resin synthetic in the used diamines are the siloxane diamine of formula (II).Be difficult to obtain can be at the bonding film that is attached to semiconductor wafer below 100 ℃ or be difficult to the tendency that do not have burr ground to rupture when bonding film is stretched if the ratio of the siloxane diamine of formula (II) less than 30 quality %, then has.Based on identical viewpoint, the ratio of the siloxane diamine of formula (II) is more preferably more than the 40 quality %, more preferably more than the 50 quality %.
Used diamines both can only contain the siloxane diamine of formula (II) in polyimide resin synthetic, also can also contain at least a compound in the siloxane diamine beyond the siloxane diamine that is selected from aliphatic diamine, aromatic diamine and formula (II).As aliphatic diamine, for example can enumerate ethylenediamine, 1,3-diaminopropanes, 1,4-diaminobutane, 1,5-diaminourea pentane, 1,6-diamino hexane, 1,7-diaminourea heptane, 1,8-diaminourea octane, 1,9-diaminourea nonane, 1,10-diamino decane and 1,12-diaminourea dodecane.As aromatic diamine, for example can enumerate o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine (PPD), 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl ether, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, 3,3 '-diamino-diphenyl difluoromethane, 3,4 '-diamino-diphenyl difluoromethane, 4,4 '-diamino-diphenyl difluoromethane, 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino-diphenyl thioether, 3,4 '-diamino-diphenyl thioether, 4,4 '-diamino-diphenyl thioether, 3,3 '-diamino-diphenyl ketone, 3,4 '-diamino-diphenyl ketone, 4,4 '-diamino-diphenyl ketone, 2, two (3-aminophenyl) propane of 2-, 2-(3-aminophenyl)-2-(4 '-aminophenyl) propane, 2, two (4-aminophenyl) propane of 2-, 2, two (aminophenyl) HFC-236fa of 2-, 2-(3-aminophenyl)-2-(4 '-aminophenyl) HFC-236fa, 2, two (4-aminophenyl) HFC-236fa of 2-, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 4-, 3,3 '-(1,4-phenylene two (1-methyl ethylidene)) benzidine, 3,4 '-(1,4-phenylene two (1-methyl ethylidene)) benzidine, 4,4 '-(1,4-phenylene two (1-methyl ethylidene)) benzidine, 2, two (4-(3-amino-benzene oxygen) phenyl) propane of 2-, 2, two (4-(4-amino-benzene oxygen) phenyl) propane of 2-, 2, two (4-(3-amino-benzene oxygen) phenyl) HFC-236fa of 2-, 2, two (4-(4-amino-benzene oxygen) phenyl) HFC-236fa of 2-, two (4-(3-amino-benzene oxygen) phenyl) thioether, two (4-(4-amino-benzene oxygen) phenyl) thioether, two (4-(3-amino-benzene oxygen) phenyl) sulfone, and two (4-(4-amino-benzene oxygen) phenyl) sulfone.
Can for example represent with the siloxane diamine of formula (II) and the siloxane diamine of usefulness by following general formula (III).In the formula (III), Q 1And Q 2Represent independently that respectively phenylene or carbon number are 1～5 alkylidene (wherein, p represented that carbon number was 4～6 alkylidene at 1 o'clock), Q 3, Q 4, Q 5And Q 6Represent independently that respectively carbon number is that 1～5 alkyl, carbon number are 1～5 alkoxyl, phenyl or phenoxy group, p represents 1～50 integer.
Figure G2008800095998D00101
As the siloxane diamine of formula (III), be 1 o'clock at p, have 1,1,3,3-tetramethyl-1, two (4-aminophenyl) disiloxane of 3-, 1,1,3,3-four phenoxy groups-1, two (2-amino-ethyl) disiloxane of 3-, 1,1,3,3-tetramethyl-1,3-two (the amino butyl of 4-) disiloxane, and 1,3-dimethyl-1,3-dimethoxy-1,3-two (the amino butyl of 4-) disiloxane, at p is 2 o'clock, has 1,1,3,3,5, the 5-vegolysen, two (4-aminophenyl) trisiloxanes of 5-, 1,1,5,5-tetraphenyl-3,3-dimethyl-1, two (3-aminopropyl) trisiloxanes of 5-, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-two (the amino butyl of 4-) trisiloxanes, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-two (the amino amyl group of 5-) trisiloxanes, 1,1,5,5-tetramethyl-3,3-dimethoxy-1, two (2-amino-ethyl) trisiloxanes of 5-, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-two (the amino butyl of 4-) trisiloxanes, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-two (the amino amyl group of 5-) trisiloxanes, 1,1,3,3,5, the 5-vegolysen, two (3-aminopropyl) trisiloxanes of 5-, 1,1,3,3,5,5-Hexaethyl-1, two (3-aminopropyl) trisiloxanes of 5-, 1,1,3,3,5,5-six propyl group-1, two (3-aminopropyl) trisiloxanes of 5-are 3～50 o'clock at p, and the compound by following chemical formulation is arranged.Also two or more kinds may be used for they.
Figure G2008800095998D00111
The viewpoint of the disposal under the room temperature of bonding film or suitableization of adhesive strength considers, the vitrification point of polyimide resin is preferably more than 30 ℃ below 80 ℃.If the vitrification point of polyimide resin is less than 30 ℃, then polyimide resin at room temperature can deliquescing, has problems aspect stable in the property disposed, keeping easily.In addition, if the vitrification point of polyimide resin surpasses 80 ℃, then having becomes is difficult in the tendency that is attached to below 100 ℃ on the wafer.Based on identical viewpoint, the vitrification point of polyimide resin is more preferably more than 40 ℃ below 80 ℃, more preferably more than 45 ℃ below 80 ℃.
The reaction that is generated polyimide resin by tetracarboxylic dianhydride and diamines can suitably be adopted the condition that is adopted usually as is known to the person skilled in the art in the synthetic reaction of polyimide resin.
Adhesive film for semiconductor also can also contain Thermocurable composition and/or filler except above-mentioned polyimide resin.The Thermocurable composition is to utilize the composition that adds the thermosetting three-dimensional network structure and solidify, and for example is made of heat-curing resin and curing agent thereof and/or curing accelerator.By using the Thermocurable composition, just have the tendency that the shear bond power under the high temperature uprises.But in a single day owing to use the Thermocurable composition, then the peeling adhesion force under the high temperature has the tendency of reduction on the contrary, therefore preferably according to application target, suitably selects whether to use the Thermocurable composition.
The amount of heat-curing resin is preferably 1～100 weight portion with respect to polyimide resin 100 weight portions, more preferably 1～50 weight portion.If surpass 100 weight portions, then have the tendency of film formation property reduction.
Heat-curing resin is preferably from epoxy resin and have the imide compound of 2 Thermocurable imides and select.
The epoxy resin that uses as heat-curing resin is the compound with the epoxy radicals more than 2.Consider the glycidyl ether type epoxy resin of preferred phenol from the aspect of curable or solidfied material characteristic.As the glycidol fundamental mode epoxy resin of phenol, can enumerate the condensation product of bisphenol-A, bisphenol-A D, bisphenol S, Bisphenol F or halogenation bisphenol-A and chloropropylene oxide; The glycidyl ether of phenol novolac resin; The glycidyl ether of cresols novolac resin; And the glycidyl ether of bisphenol-A phenolic varnish gum.Preferred use epoxide equivalent is 100～500 epoxy resin.
When using epoxy resin,, preferably use phenolic resins as its curing agent as heat-curing resin.The OH equivalent of phenolic resins is preferably 50～600.Phenolic resins is the compound with the phenol hydroxyl more than 2.As the concrete example of phenolic resins, can enumerate phenol novolac resin, cresols novolac resin, bisphenol-A phenolic varnish gum, poly-to vinylphenol and phenyl aralkyl resin.Under the situation of using phenolic resins, its amount is preferably 1～300 weight portion with respect to epoxy resin 100 weight portions, more preferably 1～150 weight portion, more preferably 1～120 weight portion.If surpass 300 weight portions, then have the tendency that curable reduces.
As with the curing agent or the curing accelerator of epoxy resin combination, except phenolic resins, for example can use imidazoles, cyanoguanidine derivative, dicarboxyl acid dihydrazide, triphenylphosphine, tetraphenylphosphoniphenolate tetraphenyl borate, 2-ethyl-4-methylimidazole-tetraphenyl borate and 1,8-diazabicyclo [5.4.0] hendecene-7-tetraphenyl borate.They also can be also with two or more.The amount of curing accelerator is preferably 0～50 weight portion with respect to epoxy resin 100 weight portions, more preferably 0.1～50 weight portion, more preferably 0.1～20 weight portion.If the amount of curing accelerator surpasses 50 weight portions, then have the tendency that storage stability reduces.
Under the situation that epoxy resin, phenolic resins and curing accelerator are used in combination, the composition of adhesive film for semiconductor for example is polyimide resin: 100 weight portions, epoxy resin: 1～100 weight portion, phenolic resins: with respect to epoxy resin 100 weight portions is 1～600 weight portion, curing accelerator: with respect to epoxy resin 100 weight portions is 0～50 weight portion.
As the example that can be used as the imide compound of heat-curing resin, adjacent penylene bismaleimides, a penylene bismaleimides are arranged, to penylene bismaleimides, 1, two (to the maleimide cumyl) benzene, 1 of 4-, two (a maleimide cumyl) benzene of 4-and with following formula (IV), (V) or (VI) imide compound of expression.
Figure G2008800095998D00131
In the formula (IV), X 1Expression-O-,-CH 2-,-CF 2-,-SO 2-,-S-,-CO-,-C (CH 3) 2-or-C (CF 3) 2-, R 11, R 12, R 13And R 14Represent hydrogen atom, low alkyl group, lower alkoxy, fluorine, chlorine or bromine, Z respectively independently 1Expression has the dicarboxylic acid residue of ethene unsaturated double-bond.
In the formula (V), X 2Expression-O-,-CH 2-,-CF 2-,-SO 2-,-S-,-CO-,-C (CH 3) 2-or-C (CF 3) 2-, R 15, R 16, R 17And R 18Represent hydrogen atom, low alkyl group, lower alkoxy, fluorine, chlorine or bromine, Z respectively independently 2Expression has the dicarboxylic acid residue of ethene unsaturated double-bond.
In the formula (VI), Z 3Expression has the dicarboxylic acid residue of ethene unsaturated double-bond, and r represents 0～4 integer.
Imide compound as formula (IV), for example have 4,4 '-bismaleimides diphenyl ether, 4,4 '-bismaleimides diphenyl methane, 4,4 '-bismaleimides-3,3 '-dimethyl-diphenyl methane, 4,4 '-bismaleimides diphenyl sulfone, 4,4 '-bismaleimides diphenylsulfide, 4,4 '-bismaleimides diphenylketone, 2, two (4-maleimide phenyl) propane, 4 of 2-, 4 '-bismaleimides diphenyl fluoromethane and 1,1,1,3,3,3-hexafluoro-2, two (4-maleimide phenyl) propane of 2-.
Imide compound as formula (V), two [4-(4-maleimide phenoxy group) phenyl] ethers are for example arranged, two [4-(4-maleimide phenoxy group) phenyl] methane, two [4-(4-maleimide phenoxy group) phenyl] fluoromethane, two [4-(4-maleimide phenoxy group) phenyl] sulfone, two [4-(3-maleimide phenoxy group) phenyl] sulfone, two [4-(4-maleimide phenoxy group) phenyl] thioether, two [4-(4-maleimide phenoxy group) phenyl] ketone, 2, two [4-(the 4-maleimide phenoxy group) phenyl] propane of 2-, and 1,1,1,3,3,3-hexafluoro-2, two [4-(the 4-maleimide phenoxy group) phenyl] propane of 2-.
In order to promote the curing of these imide compounds, also can use radical polymerization initiator.As radical polymerization initiator, acetyl group cyclohexyl sulfonyl-peroxide, peroxidating isobutyryl, benzoyl peroxide, peroxidating decoyl, acetyl peroxide, dicumyl peroxide, cumene hydroperoxide and azo isobutyronitrile etc. are arranged.The use amount of radical polymerization initiator is preferably 0.01～1.0 weight portion haply with respect to imide compound 100 weight portions.
Filler is with the fracture strength of the bonding film that improves the B-stage state and reduce tension fracture elongation rate, improve bonding film disposal, to improve heat conductivity, adjust melt viscosity, give thixotropy etc. be that purpose is used.As filler, for example can use the conductivity filler that is selected from silver powder, bronze and the copper powder; The inorganic filler that contains the nonmetal system of inorganic substances.
As the inorganic substances that constitute inorganic filler, for example can enumerate aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicates, magnesium silicate, calcium oxide, magnesium oxide, aluminium oxide, aluminium nitride, aluminium borate whisker, boron nitride, crystallinity silicon dioxide, noncrystal silicon dioxide and sb oxide.In order to improve heat conductivity, preferably use aluminium oxide, aluminium nitride, boron nitride, crystallinity silicon dioxide and noncrystal silicon dioxide.For adjusting melt viscosity or give thixotropic purpose, preferred aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicates, magnesium silicate, calcium oxide, magnesium oxide, aluminium oxide, crystallinity silicon dioxide and noncrystal silicon dioxide.In addition, in order to improve moisture-proof, preferred aluminium oxide, silicon dioxide, aluminium hydroxide and sb oxide.Also can and use multiple filler.
By increasing the content of filler, the fracture strength of the bonding film that just can raise, improve modulus of elasticity, increase toughness.But if cross the content that increases filler greatly, the durability that then has bonding film reduces, the tendency of the crackle of anti-backflow property reduction.Particularly, be used for organic substrate and so on have convex-concave surface by convered structure and semiconductor chip bonding the time, adhesive linkage destroys easily.In addition, if filler increases, then have the tendency that the temperature that bonding film attaches to semiconductor wafer can be raise.Based on this kind viewpoint, the content of filler is preferably less than 30 quality % with respect to the gross mass of adhesive film for semiconductor, more preferably less than 25 quality %, more preferably less than 20 quality %.The content of filler is preferably more than 1 weight portion with respect to polyimide resin 100 weight portions, more preferably 3 weight portions.
Adhesive film for semiconductor preferably have with semiconductor-chip-mounting in semiconductor-chip-mounting with support unit on the time desired thermal endurance and moisture-proof.For this reason, preferably carry out the test of the crackle of anti-backflow property.Adhesive strength can be estimated the crackle of anti-backflow property of adhesive film for semiconductor as index.In order to obtain the good crackle of anti-backflow property, when adhesive film for semiconductor being bonded in semiconductor wafer with the square bond area of 4 * 2mm, preferred peel strength is more than the 1.0kg/cm in the early stage, is more than the 0.5kg/cm after placing 48 hours under 85 ℃/85% the atmosphere.The peel strength at initial stage is more preferably more than the 1.3kg, more preferably 1.5kg/cm.Peel strength after placing 48 hours under 85 ℃/85% the atmosphere is more preferably more than the 0.7kg/cm, more preferably more than the 0.8kg/cm.
The tension fracture elongation rate of adhesive film for semiconductor is preferably less than 5%.Percentage elongation when in addition, the tension fracture elongation rate of adhesive film for semiconductor is preferably with respect to the maximum load of tension test less than 110%.By having this kind tensile properties, adhesive film for semiconductor just is difficult to occur burr when rupturing because of tensile stress, when utilizing method described later to make semiconductor chip, can suppress the generation of burr especially significantly.In addition, have this kind tensile properties, just can adhesive film for semiconductor be disconnected effectively and reliably with extensive magnitude seldom by making adhesive film for semiconductor.
If tension fracture elongation rate is more than 5%, then for adhesive film for semiconductor is fully disconnected, the extensive magnitude that just need make dicing tape is more than the common degree.In addition, the ratio of the percentage elongation of tension fracture elongation rate during with respect to maximum load is to cause yield situation long more than 110%, or cause constriction (necking) easily, under this situation, will have to be difficult to the tendency that when suppressing burr, adhesive film for semiconductor 2 fully disconnected.
Based on viewpoint same as described above, tension fracture elongation rate is more preferably less than 4%, more preferably less than 3.5%.Similarly, the ratio of the percentage elongation when tension fracture elongation rate and maximum load is more preferably less than 108%, more preferably less than 105%.And this ratio will reach as 100% of minimum when the percentage elongation of tension fracture elongation rate during with maximum load is consistent.
By adhesive film for semiconductor being utilized above-mentioned one-tenth assign to constitute, suitably adjust the kind and the use level of each composition, just can obtain having the adhesive film for semiconductor of above-mentioned specific tensile properties at an easy rate.
Maximum stress, maximum load percentage elongation and tension fracture elongation rate can be by using the rectangular test film of the size with wide 5mm, long 50mm, thick 25 μ m that cuts out from the adhesive film for semiconductor of B-stage state, under 25 ℃ environment, carry out tension test and obtain with following condition.
Cupping machine: SIMADZU makes 100N autoplotter " AGS-100NH "
Distance (during on-test): 30mm between chuck
Draw speed: 5mm/ minute
From utilize stress-deformation curve that tension test obtains, length between the chuck in length and when fracture between the chuck when reading maximum load, maximum load, use the measured value of these values and sample sectional area, utilize following formula to calculate maximum stress, maximum load percentage elongation and tension fracture elongation rate.
Sectional area (the m of maximum stress (Pa)=maximum load (N)/sample 2)
Percentage elongation during maximum load (%)={ (length between the chuck during maximum load (mm)-30)/30} * 100
Tension fracture elongation rate (%)={ (length between the chuck during fracture (mm)-30)/30} * 100
As a rule, a plurality of test films are measured, with the tensile properties record of its mean value as this adhesive film for semiconductor.Though consider, preferably carry out tension test under these conditions, yet also can change to other condition of the result of the test that can substantially provide identical from the viewpoint of reproducibility.
Adhesive film for semiconductor for example can utilize following method to obtain, promptly, to contain polyimide resin, Thermocurable composition, filler and dissolving or disperse the coating liquid (pasty mixture) of their organic solvent to be coated on the basement membrane, and utilize heating from epilamellar coating liquid, to remove organic solvent.Above-mentioned coating liquid can be by mixing each raw material, and the appropriate combination mixer, grind dispersion machine such as mixer, three-roll mill, ball mill and mixing method is modulated.
Organic solvent is so long as can be with organic volume of material dissolving equably, mixing or dispersion, just be not particularly limited, for example can enumerate dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone, methyl-sulfoxide, diethylene glycol dimethyl ether, toluene, benzene, dimethylbenzene, methylethylketone, oxolane, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve Ji diox.They both may be used alone, can also be used in combination two or more.
Be not particularly limited for basement membrane, get final product so long as can tolerate the heating of carrying out in order to remove organic solvent.As the example of basement membrane, can enumerate polyester film, polypropylene screen, PETG film, polyimide film, polyetherimde films, polyethers naphthoic acid ester film and methylpentene film.Also can use as basement membrane having made up the multilayer film that these films more than 2 kinds form.Silicone-based, processing such as release agent such as silica-based also can be used in the surface of basement membrane.After removing organic solvent, can directly be used as the supporter of adhesive film for semiconductor, and needn't remove basement membrane.
Adhesive film for semiconductor can also and use with the state keeping of the composite sheet of fitting with dicing tape.By adopting such composite sheet, the manufacturing process that can simplify semiconductor device.
The manufacture method of semiconductor chip
(first execution mode)
Fig. 1,2,3,4 and 5 is profiles of manufacture method of the semiconductor chip of expression first execution mode.The manufacture method of the semiconductor chip of present embodiment comprises: preparation has stacked gradually the operation (Fig. 1) of the laminated body 20 of semiconductor wafer 1, adhesive film for semiconductor 2 and dicing tape 3; Form the operation (Fig. 2,3) of grooving 40 in laminated body 20 from semiconductor wafer 1 side; The operation (Fig. 4) that adhesive film for semiconductor 2 is cut apart along grooving 40; The operation (Fig. 5) that semiconductor chip 10 is picked with adhesive film for semiconductor 2.The adhesive film for semiconductor of above-mentioned execution mode is used as adhesive film for semiconductor 2 and uses.
The laminated body 20 of Fig. 1 utilizes following method to prepare, promptly, attach adhesive film for semiconductor 2 and dicing tape 3 successively at the back side of semiconductor wafer 1, or with the composite sheet of stacked adhesive film for semiconductor 2 and dicing tape 3 with adhesive film for semiconductor 2 be positioned at semiconductor wafer 1 side towards the back side that is attached to semiconductor wafer 1.
As semiconductor wafer 1, except using monocrystalline silicon, can also use the wafer that constitutes by compound semiconductors such as polysilicon, various pottery, gallium arsenic etc.Dicing tape 3 just can use so long as the fixing annular element of usefulness had cementability that can fixation degree and can be stretched to adhesive film for semiconductor 2 is disconnected with being not particularly limited.For example, the vinyl chloride adhesive tape can be used as dicing tape.
When being attached to adhesive film for semiconductor 2 or composite sheet with it on the semiconductor wafer 1, preferably the temperature with adhesive film for semiconductor remains 0～100 ℃.By attaching adhesive film for semiconductor 2 with lower temperature like this, just can suppress the warpage of semiconductor wafer 1 and the damage that causes by the thermal process of dicing tape or grinding back surface adhesive tape fully.Based on identical viewpoint, more preferably 15 ℃～95 ℃, more preferably 20 ℃～90 ℃.
For laminated body 20, semiconductor wafer 1 being divided into a plurality of semiconductor chips 10, and adhesive film for semiconductor 2 do not cut off and the mode that keeps in the part of thickness direction, forms grooving 40 (Fig. 2) with cutting blade 4 from semiconductor wafer 1 side.In other words, semiconductor wafer 1 is fully cut off, and along the line of semiconductor wafer 1 the bonding film 2 of semiconductor is carried out hemisect.
Fig. 3 is that expression is formed near the amplification profile the grooving 40 of laminated body 20.The thickness T 1 of " hemisect " expression incision adhesive film for semiconductor 2 and the degree of depth T2 of adhesive film for semiconductor 2 satisfy the relation of T2/T1＜1.。T2/T1 is preferably 1/5～4/5, and more preferably 1/4～3/4, more preferably 1/3～2/3.If T2 diminishes, then the trend that prevents that burr from taking place is being arranged during with bonding film 2 along grooving 40 dividing semiconductors, and on the other hand, even stretching dicing tape 3, or the further projecting height that improves when picking semiconductor chip 10, also exist and be difficult to the tendency of complete dividing semiconductor with bonding film 2.In addition, big if T2 becomes, even the amount of stretching dicing tape (following according to circumstances be called " extensive magnitude " then.) little, the projecting height when perhaps picking semiconductor chip 10 is low, also has the tendency of cutting apart tube core welding film easily fully.But if T2 exceedingly becomes greatly, then the effect that suppresses of burr diminishes, thereby has the tendency that effect that the product percent of pass of semiconductor device manufacturing improves diminishes.
After forming grooving 40,, that is,, thus adhesive film for semiconductor 2 is cut apart (Fig. 4) along the upward stretching of direction (direction of the arrow of Fig. 2) of dicing tape 3 interareas with the direction that dicing tape 3 is separated from each other at a plurality of semiconductor chips 10.Consequently, semiconductor chip 10 and have the semiconductor chip that has bonding film that attaches the adhesive film for semiconductor 2 on it and be in the state that is arranged on the dicing tape 3.
Extensive magnitude is width (Breadth Maximum) R of the dicing tape 3 after stretching 1Width (Breadth Maximum) R with the dicing tape 3 at initial stage 0(with reference to Fig. 2's) is poor.This extensive magnitude is preferably 2mm～10mm, more preferably 2mm～8mm, more preferably 2mm～7mm.As described in present embodiment, form under the situation of grooving at adhesive film for semiconductor 2, owing to there is the chance of cutting off,, can reduce extensive magnitude so compare with the situation of the described later second bonding film of implementing 2 of incomplete cut-off semiconductor.
Behind stretching dicing tape 3, semiconductor chip 10 is picked (Fig. 5) with the adhesive film for semiconductor 2 that is attached to its back side.On the position of the semiconductor chip 10 that will pick, can be with dicing tape 3 from ejecting to the height of regulation with semiconductor chip 10 opposite sides.The semiconductor chip 10 that has picked can use the adhesive film for semiconductor 2 that will be attached to its back side to be equipped on various support units etc. as the tube core welding material.To narrate in the back for the operation after picking.
(second execution mode)
Fig. 6,7,8 and 9 is profiles of manufacture method of the semiconductor chip of expression second execution mode.The method of present embodiment has: preparation has stacked gradually the operation (Fig. 6～8) of the laminated body 20 of semiconductor wafer 1, adhesive film for semiconductor 2 and dicing tape 3; Stretch by the direction that dicing tape 3 is separated from each other along a plurality of semiconductor chips 10, and semiconductor wafer 1 is divided into a plurality of semiconductor chips 10 and the dividing semiconductor operation (Fig. 9) with bonding film 2; The operation that semiconductor chip 10 is picked with adhesive film for semiconductor 2.
The operation of preparing laminated body 20 comprises: along utilize laser processing with semiconductor wafer 1 be divided into a plurality of semiconductor chips 10 line 50 (below be called " cutting apart preset lines ".) form the operation (Fig. 6) of the upgrading 1a of portion in the inside of semiconductor wafer 1; Attach the operation (Fig. 7) of adhesive film for semiconductor 2 at the semiconductor wafer 1 that has formed the 1a of upgrading portion; And the operation (Fig. 8) that attaches dicing tape 3 at adhesive film for semiconductor 2.
Utilizing laser processing to form in the operation of the upgrading 1a of portion, along cutting apart preset lines 50 irradiating lasers 90 (Fig. 6 (a)).This laser processing can utilize in the method for known so-called stealthy cutting the common condition that adopts to carry out.Utilize laser processing, form the upgrading 1a of portion in the inside of semiconductor wafer 1.
, as Fig. 7,8 shown in, on semiconductor wafer 1 successively attach adhesive film for semiconductor 2 and dicing tape 3, obtain laminated body 20 thereafter.
The operation that obtains laminated body 20 is not limited to the order of present embodiment.For example, also can after having attached adhesive film for semiconductor, semiconductor wafer utilize laser processing to form upgrading portion.
After having obtained laminated body 20, stretch by the direction (direction of the arrow of Fig. 8 (b)) that dicing tape 3 is separated from each other along a plurality of semiconductor chips 10, thereby semiconductor wafer 1 is divided into a plurality of semiconductor chips 10, and adhesive film for semiconductor 2 is cut apart (Fig. 9) along the 1a of upgrading portion.
According to present embodiment, semiconductor wafer 1 and adhesive film for semiconductor 2 can be cut apart by the stretching of dicing tape, and need not to utilize cutting blade to cut off.According to this method, do not need to utilize cutting blade side by side to cut off semiconductor wafer 1 and adhesive film for semiconductor 2, therefore can improve the speed of the singualtion of semiconductor wafer, can also suppress the generation of burr.
Under the situation of present embodiment, the extensive magnitude of dicing tape 3 is preferably 5～30mm, more preferably 10～30mm, more preferably 10～20mm.Be difficult to tendency that semiconductor wafer 1 and adhesive film for semiconductor 2 are fully disconnected if extensive magnitude less than 5mm, then has,, then have the tendency that causes easily along cutting apart the part fracture beyond the preset lines if surpass 30mm.
In addition, under the situation of present embodiment, the speed of stretching dicing tape 3 (expansion speed) is preferably 10～1000mm/ second, 10～100mm/ second more preferably, more preferably 10～50mm/ second.Be difficult to tendency that semiconductor wafer 1 and adhesive film for semiconductor 2 are fully disconnected if expansion speed less than 10mm/ second, then has,, then have the tendency that causes easily along cutting apart the part fracture beyond the preset lines if surpass 1000mm/ second.
As above shown in the explanation, utilize that the method for first execution mode or second execution mode obtains, with the semiconductor chip 10 that adhesive film for semiconductor 2 picks, for example constitute the semiconductor element of IC, LSI and so on.Semiconductor chip 10 for example can be bonded on the support unit by the adhesive film for semiconductor 2 that is attached to its back side.As support unit, for example can enumerate lead frames such as 42 alloy lead wire frames and copper lead frame; The resin molding that forms by epoxy resin, polyimide resin and maleimide resin etc.; On glass nonwoven fabrics or glass woven fabric epoxy resin-impregnated, polyimides be resin and maleimide be heat-curing resin such as resin and make its curing and substrate; And ceramic substrates such as glass substrate and aluminium oxide.
Can be bonding between the semiconductor chip by adhesive film for semiconductor.Figure 10 is the profile that expression utilizes an execution mode of the semiconductor device that this method obtains.Semiconductor device 100 shown in Figure 10 has: the semiconductor chip 10b that has the base material (support unit) 7 of wiring, is bonded in the semiconductor chip 10a on the base material 7 that has wiring by adhesive film for semiconductor 2 and is bonded in semiconductor chip 10a by adhesive film for semiconductor 2.Semiconductor chip 10a and 10b utilize closing line 8 to be connected with the wiring of the base material 7 that has wiring.In addition, semiconductor chip 10a and 10b are by sealing resin layer 9 sealings of burying these semiconductor chips underground.
Bonding between the bonding and semiconductor chip of semiconductor chip and support unit for example can be in clamping between semiconductor chip and the support unit or between the semiconductor chip under the state of adhesive film for semiconductor, carry out with 60～300 ℃ of heating 0.1～300 second.
Contain at adhesive film for semiconductor 2 under the situation of heat-curing resin, the semiconductor chip after the preferred caking and promote adhesive film for semiconductor with by the driving fit of convered structure or curing, thereby increase the intensity at junction surface.The heating of this moment as a rule is to carry out under 60～220 ℃ 0.1～600 minute as long as suitably adjust according to the composition of bonding film.Carrying out under the resin-sealed situation, also can utilize the heating of the curing process of sealing resin.
Embodiment
Below, enumerate embodiment the present invention is carried out more specific description.But the present invention is not limited to following embodiment.
1. the making of adhesive film for semiconductor
Embodiment 1
In the four-hole boiling flask of the 500ml with thermometer, mixer and calcium chloride tube, add as 1 of diamines, two (3-aminopropyl) tetramethyl disiloxanes (0.1mol) of 3-and as the N-N-methyl-2-2-pyrrolidone N-150g of solvent stir down at 60 ℃.Behind two amine solvents, little by little add 1,10-(decamethylene) two (trimelitic dianhydride) is (0.02mol) with 4, and the two phthalic anhydrides (0.08mol) of 4 '-oxygen were 60 ℃ of reactions 3 hours.Be blown into N thereafter, 2170 ℃ of heating down, utilized azeotropic that the water in the system is removed with the part of solvent in the time of gas with 3 hours.The nmp solution of the polyimide resin that will get except that anhydrating is used for the making of bonding film.
In the nmp solution (containing polyimide resin 100 weight portions) of the polyimide resin that utilizes aforesaid operations to obtain, add cresols phenolic resin varnish (changing into system of Dongdu) 4 weight portions, 4,4 '-[1-[4-[1-(4-hydroxy phenyl)-1-Methylethyl] phenyl] ethylidine] bis-phenol (Honshu chemistry is made) 2 weight portions, tetraphenylphosphoniphenolate tetraphenyl borate (tetraphenylphosphoniumtetraphenylborate) (the Tokyo system of changing into) 0.5 weight portion.Then, quality with respect to all solids composition reaches 12 quality % ground adding boron nitride filler (water island alloy is iron), quality with respect to all solids composition reaches 3 quality % ground adding Aerosil (Japanese: filler R972 (Japanese Aerosil system) ア エ ロ ジ Le), fully mixing, obtain varnish.The varnish of being modulated is coated the PETG film that lift-off processing finishes, heated 30 minutes down at 80 ℃, next 120 ℃ of heating 30 minutes, thereafter, under room temperature (25 ℃), divest the PETG film, obtain the bonding film of thick 25 μ m.
Embodiment 2～4
The mix proportion of the raw material except with the synthesis of polyimides resin time changes to each shown in the table 1 to be formed (weight portion), has obtained bonding film in the same manner with embodiment 1.
Comparative example 1
Except the mix proportion with raw material changes to the composition shown in the table 1 (weight portion), obtained the nmp solution of polyimide resin in the same manner with embodiment 1.Use the nmp solution of the polyimide resin of gained, the mix proportion of boron nitride filler is made as 9 quality %, do not use the aerosil filler, in addition, obtained bonding film in the same manner with embodiment 1 with respect to the weight of all solids composition.
Comparative example 2
Except the mix proportion with raw material changes to the composition shown in the table 1 (weight portion), obtained the nmp solution of polyimide resin in the same manner with embodiment 1.Use the nmp solution of the polyimide resin of gained, the mix proportion of boron nitride filler is made as 10 quality %, do not use the aerosil filler, in addition, obtained bonding film in the same manner with embodiment 1 with respect to the weight of all solids composition.
Comparative example 3
Except the mix proportion of boron nitride filler being made as 40 quality % with respect to the weight of all solids composition, do not use beyond the aerosil filler, obtained bonding film in the same manner with embodiment 1.
Comparative example 4
Except the mix proportion with raw material changes to the composition shown in the table 1 (weight portion), obtained the nmp solution of polyimide resin in the same manner with embodiment 1.Use the nmp solution of the polyimide resin of gained, the mix proportion of boron nitride filler is made as 28 quality %, do not use the aerosil filler, in addition, obtained bonding film in the same manner with embodiment 1 with respect to the weight of all solids composition.
Comparative example 5
Except the mix proportion of boron nitride filler being made as 50 quality % with respect to the weight of all solids composition, do not use beyond the aerosil filler, obtained bonding film in the same manner with embodiment 1.
Comparative example 6
Except the mix proportion of boron nitride filler being made as 57 quality % with respect to the weight of all solids composition, do not use beyond the aerosil filler, obtained bonding film in the same manner with embodiment 1.
[table 1]
Figure G2008800095998D00231
In the table 1, the brevity code of raw material is represented following acid anhydrides or diamines.
(acid anhydrides)
ODPA:4, the two phthalic anhydrides (Manac corporate system) of 4 '-oxygen
DBTA:1,10-(decamethylene) two (trimelitic dianhydride) (the dark fund system of changing into)
BPADA:2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydrides (the dark fund system of changing into) of 2-
(diamines)
LP7100:1, two (3-aminopropyl) tetramethyl disiloxanes (chemical company of SHIN-ETSU HANTOTAI system) of 3-
B 12:4,9-dioxadecane-1,12-diamines (BASF AG's system)
D2000: polyoxygenated propane diamine 2000 (BASF AG's system)
BAPP:2,2 pairs-(4-(4-amino-benzene oxygen) phenyl) propane (Wakayama refine industrial group's system)
2. the evaluation of bonding film
(1) maximum stress, maximum load percentage elongation and tension fracture elongation rate
The rectangular test film that use cuts out from the bonding film of B-stage state (wide 5mm, long 50mm) has carried out tension test.From the stress-deformation curve of gained, maximum stress, maximum load percentage elongation and tension fracture elongation rate have been obtained based on following calculating formula.Tension test is to use cupping machine (SIMADZU system 100N autoplotter, AGS-100NH), in 25 ℃ atmosphere, carries out apart from the condition of 30mm, draw speed 5mm/min. between the chuck during with on-test.
Sectional area (the m of maximum stress (Pa)=maximum load (N)/sample 2)
Maximum load percentage elongation (%)=[(length between the chuck under the maximum load (mm)-30)/30] * 100
Tension fracture elongation rate (%)=[(length between the chuck during fracture (mm)-30)/30] * 100
Figure 11 is the figure of stress-deformation curve of the bonding film of expression embodiment 1, and Figure 12 is the figure of stress-deformation curve of the bonding film of expression comparative example 1.Among the figure, length-30 between elongation (mm)=chuck.Calculate the maximum load percentage elongation according to the elongation corresponding with maximum load Pmax, the elongation E that drops to 0 time point according to test film fracture back, load calculates tension fracture elongation rate.
(2) wafer attaches temperature
Use is warmed to the hot rolling laminator (0.3m/ minute, 0.3MPa) of the temperature of regulation, bonding film and the semiconductor wafer of wide 10mm are fitted, thereafter, to bonding film in 25 ℃ atmosphere, minute peel the disbonded test of bonding film with 90 ° of stretching angles, draw speed 50mm/, obtain peel strength.Disbonded test is to use TOYOBALDWIN system UTM-4-100 type TENSILON to carry out.The design temperature of hot rolling laminator is heated up 10 ℃ from 40 ℃ at every turn, and the minimum temperature in the hot rolling laminator temperature during with the peel strength more than the acquisition 20N/m is made as wafer and attaches temperature.
(3) vitrification point
180 ℃ of down heating 1 hour and in the bonding film that solidified, cut out the sample of about 4 * 20mm size.To this sample, use Seiko electronics system TMA120, with Extension, programming rate: 5 ℃/min, the condition of sample measured length: 10mm are measured the displacement of sample, have obtained representing the curve of the relation of displacement and temperature.From the curve of gained, obtain vitrification point.Figure 13 is the curve chart of an example of the relation of expression displacement and temperature.As shown in Figure 13, draw 2 tangent lines with the contact of a curve of the part of the front and back in vitrifying zone, their temperature of intersection point is made as vitrification point (Tg).
(4) room temperature adhesive strength
Use Rhesca Co., Ltd. system tack meter, utilize the method put down in writing among the JISZO237-1991 (probe diameter 5.1mm, to peel speed 10mm/s, contact load 100gf/cm 2, time of contact 1s), 25 ℃ of adhesive strength of having measured the bonding film of B-stage state.Consider that from the viewpoint of operability 25 ℃ of following adhesive strength are preferably less than 5gf.
(5) peel strength (chip peels intensity)
With the silicon wafer of thick 400 μ m the degree of depth, and in dorsal part direction side, apply power cutting, prepare to form the silicon of 4mm * 2mm of the pawl of wide 150 μ m thus at circumference from its face side hemisect to 250 μ m.The bonding film that clamping cuts out with 4mm * 2mm size between this silicon and 42 alloy lead wire frames.Integral body is applied the load of 200gf, 160 ℃ of following crimping 5 seconds, and by 180 ℃ down heating solidified after making bonding film in 60 minutes.Then, use and improved the determinator shown in Figure 14 15 of recommending meter (push pullgage), the chip when having measured heating in 260 ℃, 20 seconds peels intensity.Determinator 15 has heat dish 14, is positioned over the die-cushion (die-pad) 13 on this heat dish 14 and recommends meter 12.On the die-cushion 13 of determinator 15, place sample, install at the pawl of silicon and recommend meter 12 and carried out the mensuration that chip peels intensity.To initial and implemented under 85 ℃, 85%RH environment, to place the mensuration that sample after 48 hours the hot and humid processing carries out this peel strength.Can measure the face adhesive strength of bonding film according to this mensuration.This numerical value is high more, and the backflow crackle is difficult to take place more.
(6) crackle of anti-backflow property
To be cut into the square silicon of 5mm and have engaging with the circuit board that is formed with wiring on surface of the bonding film that is pasted on this silicon as the polyimide film (thickness 25 μ m) of base material with bonding film silicon.Then, on this silicon, engage the square silicon of 5mm with other bonding films.
For resulting 10 samples, make it by reach 260 ℃ and the IR reflow ovens that under this temperature, keeps the mode in 20 seconds to set according to surface temperature, then, implement to place down in room temperature (25 ℃) for twice the processing of cooling repeatedly.Utilize the crackle in the sample after range estimation and ultrasonic microscope are observed processing, confirm the generation state of the crackle of substrate/chip chamber and chip/chip chamber.The result estimates anti-backflow crackle according to following benchmark according to the observation.
A: do not see all that in whole samples crackle produces.
C: in the sample more than 1, crack.
[table 2]
[table 2]
Figure G2008800095998D00261
(7) breaking property, chip crackle and burr
The bonding film that to make in the above embodiments or comparative example is fitted in semiconductor wafer, utilize following " full cutting ", the method for " hemisect " or " laser cutting " that semiconductor wafer is divided into semiconductor chip, and confirmed the generation state of breaking property, chip crackle and the burr of bonding film at this moment.In arbitrary method, all vinyl chloride adhesive tape (thick 90 μ m) is used as dicing tape.
Full cutting
Use hot rolling laminator (JCM corporate system DM-300H, 0.3m/ minute, 0.3MPa), under the wafer attaching temperature of table 1, each bonding film is attached to the thick semiconductor wafer of 50 μ m.Then, under the condition of 80 ℃ of hot plate temperatures, dicing tape is laminated on the bonding film, has made cutting sample.Attach the annular element of stainless steel at the dicing tape circumference, and use DISCO corporate system DFD-6361 that cutting sample is cut off.Cut-out is to adopt single butt formula of finishing processing with 1 piece of blade, is that NBC-ZH104F-SE 27HDBB, rotating speed of flail are 45 at blade, carries out under the condition of 000rpm, cut-off velocity 50mm/s.The blade cuts degree of depth (cutting groove depth) during cut-out is for cutting off the height 80 μ m of bonding film fully.Next, under the state that annular element is fixing, utilize expansion instrument stretching dicing tape.Expansion speed is 10mm/s, and extensive magnitude is 3mm.
Hemisect
The blade cuts degree of depth (cutting groove depth) is made as do not cut off and in tube core welding film, remain with the height 100 μ m of 10 μ m thickness parts, in addition, test with the condition identical with above-mentioned full cutting.
Laser cutting
(thickness 50 μ m) carry out laser radiation to semiconductor wafer, and portion forms upgrading portion along the line that is divided into semiconductor chip within it.Then, paste bonding film and dicing tape successively, attach the annular element of stainless steel at the peripheral part of dicing tape according to the order identical with full cutting.Then, utilize the expansion instrument dicing tape that under the state of having fixed annular element, stretches.Expansion speed is 30mm/s, and extensive magnitude is 15mm.
Breaking property
Behind the stretching dicing tape, utilize the bonding film of observation by light microscope whether to rupture, obtain the not ratio of the length of the part of fracture fully in the total length of section, utilize following benchmark with this ratio classification and estimated breaking property.In addition, under the situation of full cutting, utilize cutting blade to cut off bonding film, therefore do not carry out the evaluation of breaking property.
More than the AA:98%
More than the A:90%
B:50% is above and less than 90%
C: less than 50%
The chip crackle
Behind the stretching dicing tape, utilize the generation state of observation by light microscope chip crackle.Obtain the length of the chip crackle that on the face of the opposite side with bonding film of semiconductor chip, produces, utilize following benchmark the length classification of chip crackle to be estimated the generation state of chip crackle.
AA: less than 5 μ m
More than the A:5 μ m and less than 10 μ m
More than the B:10 μ m and less than 25 μ m
More than the C:25 μ m
Burr
Behind the stretching dicing tape, semiconductor chip is picked with bonding film.Utilize the end face of the semiconductor chip that has bonding film that observation by light microscope picks, confirmed the generation state of burr.
AA: the length of burr is less than 20 μ m
A: the length of burr is more than the 20 μ m and less than 40 μ m
B: the length of burr is more than the 40 μ m and less than 100 μ m
C: the length of burr is more than the 100 μ m
[table 3]
[table 3]
Figure G2008800095998D00281
Used to utilize and contained 4 of 50 quality %, the tetracarboxylic dianhydride of the two phthalic anhydrides of 4 '-oxygen, with contain 30 quality % above 1, the bonding film of the embodiment 1～4 of the polyimide resin that the reaction of the diamines of two (3-aminopropyl) tetramethyl disiloxanes of 3-obtains can be attached to semiconductor wafer below 100 ℃.In addition, the bonding film of embodiment 1～4 all demonstrates good breaking property.In addition, the bonding film of embodiment 1～4 is also very excellent aspect the crackle of anti-backflow property, owing at room temperature have the adhesive strength of appropriateness, and therefore also very excellent aspect operability.
Adopted and do not used 4, the two phthalic anhydrides of 4 '-oxygen and the bonding film of comparative example 1～3 of polyimide resin can not be attached to semiconductor wafer below 100 ℃, in addition, do not demonstrate enough breaking properties.Though the bonding film of comparative example 6 uses the polyimide resin identical with embodiment 3, yet because the content of filler is many, so can't be attached to semiconductor wafer below 100 ℃.Though the breaking property during the bonding film hemisect of comparative example 3 is good, yet the breaking property during laser cutting is abundant inadequately.In addition, the bonding film of comparative example 3 has produced crackle in substrate/chip in the test of the crackle of anti-backflow property.
Adopted and do not used 4, though the two phthalic anhydrides of 4 '-oxygen and the bonding film of comparative example 4 of polyimide resin can be attached to semiconductor wafer below 100 ℃, yet because vitrification point is low, so adhesive strength is too high under the room temperature, counteracts for operability.In addition, the bonding film of comparative example 4 is also abundant inadequately aspect breaking property.
The bonding film of comparative example 6 that use the polyimide resin identical with comparative example 4, has increased the content of filler can't be attached to semiconductor wafer under the temperature below 100 ℃, in addition, do not demonstrate enough breaking properties.In addition, in the test of the crackle of anti-backflow property, in substrate/chip, produced crackle.
Though use the polyimide resin identical with embodiment 3 the bonding film of comparative example 6 demonstrate good breaking property, yet because the content of filler is many, so can't be attached to semiconductor wafer below 100 ℃.In addition, in the test of the crackle of anti-backflow property, in substrate/chip, produced crackle.
Can clearly confirm from above experimental result, can be attached to semiconductor wafer below 100 ℃, and can in the generation that suppresses chip crackle or burr fully, from semiconductor wafer, obtain semiconductor chip with good product percent of pass.

Claims (8)

1. semiconductor adhering film,
It contains polyimide resin, and can be attached at semiconductor wafer below 100 ℃, described polyimide resin can utilize with the ratio more than the 50 overall quality % and contain by 4 of following chemical formula (I) expression, the tetracarboxylic dianhydride of the two phthalic anhydrides of 4 '-oxygen obtains with the reaction that contains the diamines of the siloxane diamine of being represented by following general formula (II) with the ratio more than the 30 overall quality %
Figure A2008800095990002C1
In the formula (II), R represents that carbon number is that 1～5 alkyl, carbon number are 1～5 alkoxyl, phenyl or phenoxy group, can be identical or different with a plurality of R in a part, and n and m represent 1～3 integer respectively independently.
2. semiconductor adhering film according to claim 1, wherein,
The vitrification point of described polyimide resin is more than 30 ℃, below 80 ℃.
3. semiconductor adhering film according to claim 1, wherein,
Described semiconductor also contains Thermocurable composition and filler with adhering film,
The content of described filler uses the quality of adhering film less than 30 quality % with respect to this semiconductor.
4. semiconductor adhering film according to claim 1, it is used for the manufacture method of following semiconductor chip,
The manufacture method of described semiconductor chip has:
Prepare the operation of duplexer, semiconductor wafer, semiconductor are stacked gradually with adhering film and dicing tape, according to described semiconductor wafer is divided into a plurality of semiconductor chips, and the mode of described semiconductor not cut off with at least a portion of the thickness direction of adhering film and keeping forms grooving from described semiconductor wafer side;
By described dicing tape is stretched along direction that described a plurality of semiconductor chip is separated from each other, and the operation that described semiconductor is cut apart along described grooving with adhering film.
5. semiconductor adhering film according to claim 1, it is used for the manufacture method of following semiconductor chip,
The manufacture method of described semiconductor chip has:
Prepare the operation of duplexer, semiconductor wafer, semiconductor are stacked gradually with adhering film and dicing tape, utilize laser processing to form upgrading portion at described semiconductor wafer along the line that described semiconductor wafer is divided into a plurality of semiconductor chips;
By described dicing tape is stretched along direction that described a plurality of semiconductor chip is separated from each other, and the operation that described semiconductor wafer is divided into described a plurality of semiconductor chip and described semiconductor is partly cut along described upgrading with adhering film.
6. composite sheet,
It has the dicing tape that each described semiconductor is used adhering film and is laminated in the one side side of this semiconductor usefulness adhering film in the claim 1～5.
7. the manufacture method of a semiconductor chip has:
Prepare the operation of duplexer, each described semiconductor in semiconductor wafer, the claim 1～3 is stacked gradually with adhering film and dicing tape, according to described semiconductor wafer is divided into a plurality of semiconductor chips, and the mode of described semiconductor not cut off with at least a portion of the thickness direction of adhering film and keeping forms grooving from described semiconductor wafer side;
By described dicing tape is stretched along direction that described a plurality of semiconductor chip is separated from each other, and the operation that described semiconductor is cut apart along described grooving with adhering film.
8. the manufacture method of a semiconductor chip has:
Prepare the operation of duplexer, each described semiconductor in semiconductor wafer, the claim 1～3 is stacked gradually with adhering film and dicing tape, utilize laser processing to form upgrading portion at described semiconductor wafer along the line that described semiconductor wafer is divided into a plurality of semiconductor chips;
By described dicing tape is stretched along direction that described a plurality of semiconductor chip is separated from each other, and the operation that described semiconductor wafer is divided into described a plurality of semiconductor chip and described semiconductor is partly cut along described upgrading with adhering film.
CN 200880009599 2007-04-06 2008-03-31 Adhesive film for semiconductor, composite sheet, and method for producing semiconductor chip using them Pending CN101641766A (en)

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CN106914697A (en) * 2011-01-13 2017-07-04 浜松光子学株式会社 Laser processing
CN108695260A (en) * 2017-03-29 2018-10-23 株式会社东芝 Semiconductor device and its manufacturing method
CN111554781A (en) * 2012-03-19 2020-08-18 亮锐控股有限公司 Singulation of light emitting devices before and after phosphor application

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106914697A (en) * 2011-01-13 2017-07-04 浜松光子学株式会社 Laser processing
CN106914697B (en) * 2011-01-13 2019-03-15 浜松光子学株式会社 Laser processing
US10532431B2 (en) 2011-01-13 2020-01-14 Hamamatsu Photonics K.K. Laser processing method
CN111554781A (en) * 2012-03-19 2020-08-18 亮锐控股有限公司 Singulation of light emitting devices before and after phosphor application
CN111554781B (en) * 2012-03-19 2024-04-12 亮锐控股有限公司 Singulation of light emitting devices before and after phosphor application
CN108695260A (en) * 2017-03-29 2018-10-23 株式会社东芝 Semiconductor device and its manufacturing method
CN108695260B (en) * 2017-03-29 2021-09-28 株式会社东芝 Semiconductor device and method for manufacturing the same

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