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WO2012032959A1 - Film pour dispositif à semi-conducteurs et dispositif à semi-conducteurs - Google Patents

Film pour dispositif à semi-conducteurs et dispositif à semi-conducteurs Download PDF

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Publication number
WO2012032959A1
WO2012032959A1 PCT/JP2011/069473 JP2011069473W WO2012032959A1 WO 2012032959 A1 WO2012032959 A1 WO 2012032959A1 JP 2011069473 W JP2011069473 W JP 2011069473W WO 2012032959 A1 WO2012032959 A1 WO 2012032959A1
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WO
WIPO (PCT)
Prior art keywords
film
dicing
adhesive
semiconductor device
adhesive film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/069473
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English (en)
Japanese (ja)
Inventor
康弘 天野
剛一 井上
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
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Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Priority to CN201180042794.2A priority Critical patent/CN103081068B/zh
Priority to KR1020117027458A priority patent/KR101190467B1/ko
Publication of WO2012032959A1 publication Critical patent/WO2012032959A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67132—Apparatus for placing on an insulating substrate, e.g. tape

Definitions

  • the present invention relates to a film for a semiconductor device and a semiconductor device manufactured using the film for a semiconductor device.
  • silver paste is used for fixing a semiconductor chip to a lead frame or an electrode member in a manufacturing process of a semiconductor device.
  • the fixing process is performed by applying a paste adhesive on a die pad or the like of the lead frame, mounting a semiconductor chip on the lead adhesive, and curing the paste adhesive layer.
  • paste adhesives have large variations in coating amount and coating shape due to their viscosity behavior and deterioration.
  • the thickness of the paste-like adhesive formed is not uniform, and the reliability of the fixing strength related to the semiconductor chip is poor. That is, when the application amount of the paste adhesive is insufficient, the bonding strength between the semiconductor chip and the electrode member is lowered, and the semiconductor chip is peeled off in the subsequent wire bonding process.
  • the application amount of the paste adhesive is too large, the paste adhesive is cast onto the semiconductor chip, resulting in poor characteristics, and the yield and reliability are lowered.
  • Such a problem in the adhering process becomes particularly remarkable as the semiconductor chip becomes larger. Therefore, it is necessary to frequently control the amount of paste adhesive applied, which hinders workability and productivity.
  • This adhesive film with a dicing sheet is formed by providing an adhesive layer on a supporting substrate so that the adhesive layer can be peeled off, and is formed by dicing a semiconductor wafer while being held by the adhesive layer and then stretching the supporting substrate.
  • the chip is peeled off together with the adhesive layer, and the chips are individually collected and fixed to an adherend such as a lead frame through the adhesive layer.
  • an adhesive film with a dicing sheet has been manufactured by individually bonding a dicing film and an adhesive film, due to restrictions in the manufacturing process. For this reason, from the viewpoint of preventing the occurrence of slack, winding deviation, positional deviation, voids (bubbles), etc. in each film production process, the production is performed while applying tensile tension to each film during conveyance by a roll. .
  • This type of adhesive film with a dicing sheet may be cured when placed in a high temperature and high humidity environment or stored for a long time under a load. As a result, the fluidity of the adhesive layer, the holding power against the semiconductor wafer, and the peelability after dicing are reduced. For this reason, adhesive films with dicing sheets are often transported while being stored in a frozen state at -30 to -10 ° C or refrigerated at -5 to 10 ° C, thereby enabling long-term storage of film properties. ing.
  • the adhesive film with a dicing sheet described above is processed in advance into the shape of a semiconductor wafer to be attached (for example, a circular shape) in consideration of workability such as attachment to a semiconductor wafer and attachment to a ring frame during dicing. There are those that have been pre-cut.
  • Such an adhesive film with a dicing sheet is obtained by laminating an adhesive film punched in a circular shape on a dicing film in which an adhesive layer is laminated on a substrate, and then dicing the dicing film into a circular shape corresponding to the ring frame. Manufactured by punching. Thereby, when dicing a semiconductor wafer, a ring frame can be affixed to the outer peripheral part of a dicing film, and an adhesive film with a dicing sheet can be fixed here now.
  • the pre-cut adhesive film with a dicing sheet is affixed to a long cover film at a predetermined interval, wound in a roll shape, and transported and stored as a film for manufacturing a semiconductor device.
  • the thickness of the portion where the adhesive film with a dicing sheet is laminated is larger than the thickness of the portion where the adhesive film is not laminated. Therefore, especially when the number of windings is increased or the tension at the time of winding is increased, the edge of another adhesive film with a dicing sheet is pressed against the adhesive film with another dicing sheet, and the trace is transferred. The smoothness of the adhesive film may be impaired. Such transfer marks are particularly prominent when the adhesive film is formed of a relatively soft resin, when the adhesive film is thick, and when the number of windings of the film for a semiconductor device is large.
  • voids bubbles
  • Such voids cause problems during the processing of semiconductor wafers, and may reduce the yield of manufactured semiconductor devices.
  • the present invention has been made in view of the above-described problems, and an object thereof is a semiconductor device in which an adhesive film with a dicing sheet in which an adhesive film is laminated on a dicing film is laminated on a cover film at a predetermined interval.
  • An object of the present invention is to provide a film for a semiconductor device capable of suppressing generation of a transfer mark on an adhesive film when the film is rolled up.
  • the inventors of the present application have studied a film for a semiconductor device in order to solve the conventional problems. As a result, it was found that by controlling the thickness of the cover film and the thickness of the dicing film constituting the film for semiconductor devices, it was possible to suppress the generation of transfer marks on the adhesive film, and the present invention was completed. I came to let you.
  • the film for a semiconductor device is a film for a semiconductor device in which an adhesive film with a dicing sheet in which an adhesive film is laminated on a dicing film is laminated on a cover film at a predetermined interval,
  • Ta / Tb is in the range of 0.07 to 2.5.
  • the Ta / Tb becomes thicker as the value is smaller.
  • stacked is below fixed. Therefore, generation of transfer marks can be suppressed.
  • the Ta / Tb is 0.07 or more and the thickness of the dicing film is thicker than that of the cover film, stress can be absorbed by the thickness of the cover film, and generation of transfer marks can be suppressed. it can.
  • the adhesive film with the dicing sheet and the cover film having the dicing film are bonded to the semiconductor wafer. Can be suitably peeled off.
  • the thickness Tb of the dicing film is constant, the Ta / Tb becomes thinner as the value is smaller. Since the Ta / Tb is 2.5 or less, the thickness of the cover film is a certain value or less. Therefore, the followability to the level difference between the portion where the dicing film is laminated and the portion where the dicing film is not laminated is good.
  • the Ta / Tb is 2.5 or less and the thickness of the cover film is not more than a certain value, the pressure when laminating the adhesive film with a dicing sheet on the cover film can be made uniform. Mixing can be prevented.
  • stacked sequentially on the dicing film in roll shape it suppresses that a transfer trace generate
  • the peel force F1 between the adhesive film and the cover film in a T-type peel test under conditions of a temperature of 23 ⁇ 2 ° C. and a peel speed of 300 mm / min is 0.025 to 0.075 N / 100 mm.
  • the peel force F2 between the adhesive film and the dicing film is in the range of 0.08 to 10 N / 100 mm, and F1 and F2 preferably satisfy the relationship of F1 ⁇ F2.
  • the film for semiconductor devices is manufactured while applying tensile tension to the dicing film, the adhesive film, and the cover film from the viewpoint of preventing the occurrence of loosening, winding deviation, positional deviation, voids (bubbles), and the like.
  • the film for a semiconductor device is manufactured in a state in which a tensile residual strain is present in any of the films constituting the film.
  • This tensile residual strain causes shrinkage in each film, for example, when frozen at ⁇ 30 to ⁇ 10 ° C. or transported at a low temperature of ⁇ 5 to 10 ° C. or stored for a long time.
  • the degree of shrinkage also differs.
  • the dicing film has the largest degree of shrinkage among the films, and the cover film has the smallest degree of shrinkage.
  • interfacial peeling occurs between the dicing film and the adhesive film, or a film floating phenomenon of the cover film is caused.
  • the peel force F1 between the adhesive film and the cover film is in the range of 0.025 to 0.075 N / 100 mm
  • the peel force F2 between the adhesive film and the dicing film is 0.08 to 10 N / 100 mm.
  • the cover film preferably has a thickness Ta of 10 to 100 ⁇ m.
  • the thickness Tb of the dicing film is preferably 25 to 180 ⁇ m.
  • the semiconductor device according to the present invention is manufactured using the film for a semiconductor device described above.
  • (A) is a top view which shows the outline of the film for semiconductor devices which concerns on this embodiment
  • (b) is the fragmentary sectional view. It is a fragmentary sectional view in the state where the film for semiconductor devices shown in Drawing 1 (a) and Drawing 1 (b) was rolled up. It is the schematic for demonstrating the manufacturing process of the film for semiconductor devices.
  • FIG.1 (a) is a top view which shows the outline of the film for semiconductor devices which concerns on this embodiment
  • FIG.1 (b) is the fragmentary sectional view.
  • the film 10 for a semiconductor device has a configuration in which an adhesive film 1 with a dicing sheet is laminated on a cover film 2 at a predetermined interval.
  • the dicing die-bonding film 1 has a structure in which an adhesive film 12 is laminated on a dicing film 11, and the dicing film 11 has a structure in which an adhesive layer 14 is laminated on a base material 13.
  • FIG. 2 is a partial cross-sectional view of the semiconductor device film shown in FIGS. 1A and 1B wound in a roll shape.
  • the film 10 for a semiconductor device wound in a roll shape there is a step 19 between a portion where the adhesive film 1 with a dicing sheet is laminated and a portion 18 where the adhesive film 1 is not laminated.
  • the several adhesive film 1 with a dicing sheet on the cover film 2 is laminated
  • Ta / Tb is 0.07 to 2.5 when the thickness of the cover film 2 is Ta and the thickness of the dicing film 11 is Tb.
  • the Ta / Tb is preferably from 0.1 to 2, and more preferably from 0.3 to 1.5.
  • the Ta / Tb becomes thicker as the dicing film 11 becomes smaller.
  • the semiconductor device film 10 since the Ta / Tb is 0.07 or more, it is laminated with a portion where the dicing film 11 is laminated, that is, a portion where the adhesive film 1 with a dicing sheet is laminated.
  • the step 19 with the not-shown portion 18 is below a certain level.
  • the adhesive film 12 which comprises the adhesive film 1 with a dicing sheet.
  • the Ta / Tb is 0.07 or more and the thickness of the dicing film 11 is larger than that of the cover film 2, the stress can be absorbed by the thickness of the cover film 2, and the generation of transfer marks is suppressed. can do.
  • the Ta / Tb is 0.07 or more and the thickness of the dicing film is thicker than that of the cover film, the adhesive film with the dicing sheet and the cover film having the dicing film are bonded to the semiconductor wafer. Can be suitably peeled off.
  • the Ta / Tb becomes thinner as the value is smaller.
  • the Ta / Tb is 2.5 or less, the thickness of the cover film 2 is a certain value or less. Therefore, the followability to the level difference between the portion where the dicing film 11 is laminated and the portion where the dicing film 11 is not laminated is good.
  • the Ta / Tb is 2.5 or less and the thickness of the cover film 2 is not more than a certain value, the pressure when laminating the adhesive film 1 with a dicing sheet on the cover film 2 can be made uniform. It is possible to prevent air bubbles from being mixed.
  • the film 10 for a semiconductor device it is possible to suppress generation of a transfer mark on the adhesive film 12 when the film is wound into a roll.
  • the peel force F1 between the adhesive film 12 and the cover film 2 is smaller than the peel force F2 between the adhesive film 12 and the dicing film 11.
  • the film 10 for semiconductor devices is applied with tensile tension to the dicing film 11, the adhesive film 12, and the cover film 2 from the viewpoint of preventing the occurrence of loosening, winding deviation, positional deviation, voids (bubbles), etc. in the manufacturing process. Laminated and manufactured. Therefore, each film has a tensile residual strain. This tensile residual strain causes shrinkage in each film, for example, when frozen at ⁇ 30 to ⁇ 10 ° C. or transported at a low temperature of ⁇ 5 to 10 ° C. or stored for a long time.
  • the dicing film has the largest degree of shrinkage and the cover film has the smallest degree of shrinkage.
  • the peeling force F1 and F2 are in a relationship of F1 ⁇ F2, so that the interfacial peeling between the films due to the difference in shrinkage between the films and the cover film. 2 can prevent the film floating phenomenon. Furthermore, it is possible to prevent a part or all of the adhesive film 12 from being transferred to the cover film 2.
  • the peel force F1 between the adhesive film 12 and the cover film 2 is preferably in the range of 0.025 to 0.075 N / 100 mm, more preferably in the range of 0.03 to 0.06 N / 100 mm, and 0.035 to 0. A range of 0.05 N / 100 mm is particularly preferable.
  • the peeling force F1 is less than 0.025 N / 100 mm, the adhesive film 12 and the cover film, for example, when frozen at ⁇ 30 to ⁇ 10 ° C. or transported at a low temperature of ⁇ 5 to 10 ° C. or stored for a long time 2 contracts at different shrinkage rates, which may cause a film floating phenomenon of the cover film 2.
  • the peel force F1 is greater than 0.075 N / 100 mm, the adhesive film 12 and the cover film 2 are too close to each other, so that the adhesive film 12 is bonded when the cover film 2 is peeled off or contracted.
  • the agent (details will be described later) may be transferred partially or entirely.
  • the value of the said peeling force F1 means the peeling force between the adhesive film 12 and the cover film 2 before thermosetting, when the adhesive film 12 is a thermosetting type.
  • the peel force F2 between the adhesive film 12 and the dicing film 11 is preferably in the range of 0.08 to 10 N / 100 mm, more preferably in the range of 0.1 to 6 N / 100 mm, and 0.15 to 0.4 N. Particularly preferred is within the range of / 100 mm.
  • the peeling force F2 is 0.08 N / 100 mm or more, the dicing film 11 and the adhesive film, for example, when frozen at ⁇ 30 to ⁇ 10 ° C. or transported at a low temperature of ⁇ 5 to 10 ° C. or stored for a long time 12 can be prevented from shrinking at different shrinkage rates, thereby preventing interfacial peeling between the dicing film 11 and the adhesive film 12.
  • the numerical range of the peeling force F2 includes the case where the pressure-sensitive adhesive layer in the dicing film 11 is an ultraviolet curable type and is cured to a certain extent by ultraviolet irradiation in advance. Moreover, hardening of the adhesive layer by ultraviolet irradiation may be before bonding with the adhesive film 12, and may be after bonding.
  • the peel force F3 between the cover film 2 and the dicing film 11 (adhesive layer 14) is preferably in the range of 0.025 mm to 5 N / 100 mm, more preferably in the range of 0.05 to 1 N / 100 mm. A range of 1 to 0.5 N / 100 mm is particularly preferable.
  • the peeling force F3 is 0.025 N / 100 mm or more, the dicing film 11 and the cover film, for example, when frozen at ⁇ 30 to ⁇ 10 ° C. or transported at a low temperature of ⁇ 5 to 10 ° C. or stored for a long time It is possible to prevent the film 2 from shrinking at different shrinkage rates, thereby causing the film floating phenomenon of the cover film 2.
  • the peeling force F3 is 5 N / 100 mm or less, the adhesion between the dicing film 11 and the cover film 2 can be suppressed, and it is possible to prevent the film from being removed in the process of peeling the cover film. it can.
  • the values of the peeling forces F1 to F3 are measured values in a T-type peeling test (JIS K6854-3) performed under conditions of a temperature of 23 ⁇ 2 ° C., a peeling speed of 300 mm / min, and a distance between chucks of 100 mm.
  • a tensile tester a trade name “Autograph AGS-H” (manufactured by Shimadzu Corporation) was used.
  • the base material 13 in the dicing film 11 serves as a strength matrix for the semiconductor device film 10 as well as the dicing film 11.
  • Examples of the base material 13 include low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolyprolene, polybutene, polymethylpentene, and the like.
  • the substrate 13 is preferably one having ultraviolet transparency among those exemplified above.
  • a material of the base material 13 a polymer such as a cross-linked body of the resin can be mentioned.
  • the plastic film may be used unstretched or may be uniaxially or biaxially stretched as necessary. According to the resin sheet imparted with heat shrinkability by stretching or the like, the adhesive area between the pressure-sensitive adhesive layer 14 and the adhesive film 12 is reduced by thermally shrinking the base material 13 after dicing, and the semiconductor chip can be recovered. Simplification can be achieved.
  • the surface of the substrate 13 is chemically treated by conventional surface treatments such as chromic acid treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, etc. in order to improve adhesion and retention with adjacent layers.
  • a physical treatment or a coating treatment with a primer for example, an adhesive substance described later can be performed.
  • the base material 13 can be used by appropriately selecting the same type or different types, and a blend of several types can be used as necessary. Further, in order to provide the base 13 with an antistatic ability, a conductive material vapor deposition layer having a thickness of about 30 to 500 mm made of metal, an alloy, or an oxide thereof is provided on the base 13. it can.
  • the substrate 13 may be a single layer or a multilayer of two or more types.
  • the thickness of the base material 13 is preferably 10 to 170 ⁇ m in order to ensure film transportability and prevent the base material from tearing, tearing, or plastically deforming even when the supporting base material is expanded in the bonding process. More preferably, the thickness is 50 to 150 ⁇ m, and still more preferably 100 to 130 ⁇ m.
  • the pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer 14 is not particularly limited, and for example, a general pressure-sensitive pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive can be used.
  • the pressure-sensitive adhesive is an acrylic pressure-sensitive adhesive based on an acrylic polymer from the standpoint of cleanability with an organic solvent such as ultrapure water or alcohol for electronic components that are difficult to contaminate semiconductor wafers and glass. Is preferred.
  • acrylic polymer examples include (meth) acrylic acid alkyl esters (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, Isopentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, hexadecyl ester , Octadecyl esters, eicosyl esters, etc., alkyl groups having 1 to 30 carbon atoms, especially 4 to 18 carbon atoms, such as
  • the acrylic polymer contains units corresponding to other monomer components copolymerizable with the (meth) acrylic acid alkyl ester or cycloalkyl ester, if necessary, for the purpose of modifying cohesive force, heat resistance and the like. You may go out.
  • Such monomer components include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride Acid anhydride monomers such as itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate Hydroxyl group-containing monomers such as 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate; Styrene Contains sulfonic acid groups such as phonic acid, allyl sulf
  • a polyfunctional monomer or the like can be included as a monomer component for copolymerization as necessary.
  • examples of such polyfunctional monomers include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) An acrylate etc. are mentioned. These polyfunctional monomers can also be used alone or in combination of two or more. The amount of the polyfunctional monomer used is preferably
  • the acrylic polymer can be obtained by subjecting a single monomer or a mixture of two or more monomers to polymerization.
  • the polymerization can be performed by any method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like.
  • the content of the low molecular weight substance is preferably small.
  • the number average molecular weight of the acrylic polymer is preferably 300,000 or more, more preferably about 400,000 to 3 million.
  • an external cross-linking agent can be appropriately employed for the pressure-sensitive adhesive in order to increase the number average molecular weight of an acrylic polymer as a base polymer.
  • the external crosslinking method include a method of adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, a melamine crosslinking agent, and reacting them.
  • a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, a melamine crosslinking agent, and reacting them.
  • the amount used is appropriately determined depending on the balance with the base polymer to be cross-linked and further depending on the intended use as an adhesive. Generally, it is preferable to add about 5 parts by weight or less, more preferably 0.1 to 5 parts by weight, with respect to 100 parts by weight of the base polymer.
  • additives such as conventionally well-known various tackifier and anti-aging agent, other than the said component as needed to an adhesive.
  • the pressure-sensitive adhesive layer 14 can be formed of an ultraviolet curable pressure-sensitive adhesive.
  • the UV curable pressure-sensitive adhesive can easily reduce its adhesive strength by increasing the degree of crosslinking by irradiation with ultraviolet rays, and by irradiating only the portion corresponding to the semiconductor wafer attachment portion of the pressure-sensitive adhesive layer 14 with UV irradiation. A difference in adhesive strength with other portions can be provided.
  • the tensile elastic modulus at 23 ° C. after the pressure-sensitive adhesive layer 14 is cured with ultraviolet rays is preferably in the range of 1 to 170 MPa, more preferably in the range of 5 to 100 MPa.
  • the ultraviolet irradiation is preferably performed with an ultraviolet irradiation integrated light quantity of, for example, 30 to 1000 mJ / cm 2.
  • the pressure-sensitive adhesive layer 14 can be cured without deficiency, and excessive adhesion with the adhesive film 12 can be prevented. As a result, a good pick-up property can be exhibited when picking up a semiconductor chip. Further, it is possible to prevent the adhesive of the adhesive layer 14 from adhering to the adhesive film 12 after picking up (so-called adhesive residue). On the other hand, by making the accumulated amount of ultraviolet irradiation less than 1000 mJ / cm 2, it is possible to prevent the adhesive layer 14 from being extremely reduced in adhesive force, thereby causing peeling between the adhesive film 12 and the mounted semiconductor. Prevents the wafer from falling off. Further, it is possible to prevent the chip jump of the formed semiconductor chip from occurring during the dicing of the semiconductor wafer.
  • the value of the tensile elastic modulus of the pressure-sensitive adhesive layer is based on the following measurement method. That is, a sample having a length of 30.0 mm, a width of 10.0 mm, and a cross-sectional area of 0.1 to 0.5 mm 2 is cut out from the adhesive layer 14. The sample was subjected to a tensile test in the MD direction at a measurement temperature of 23 ° C., a distance between chucks of 20 mm, and a tensile speed of 50 mm / min, and the amount of change (mm) due to the extension of the sample was measured.
  • the adhesive film 12 has a configuration formed only on the affixed portion according to the shape of the semiconductor wafer in plan view. Therefore, by curing the ultraviolet curable pressure-sensitive adhesive layer 14 in accordance with the shape of the adhesive film 12, the adhesive strength of the portion corresponding to the semiconductor wafer attachment portion can be easily reduced. Since the adhesive film 12 is affixed to the portion where the adhesive strength is reduced, the interface between the portion of the pressure-sensitive adhesive layer 14 and the adhesive film 12 has a property of being easily peeled off during pickup. On the other hand, the part which is not irradiated with ultraviolet rays has sufficient adhesive force.
  • the portion where the pressure-sensitive adhesive layer 14 is formed of an uncured ultraviolet curable pressure-sensitive adhesive sticks to the adhesive film 12 and can secure a holding force when dicing.
  • the ultraviolet curable pressure-sensitive adhesive can support the adhesive film 12 for fixing a chip-shaped semiconductor wafer (semiconductor chip or the like) to an adherend such as a substrate with a good balance of adhesion and peeling.
  • the adhesive film 12 is laminated only on the portion where the semiconductor wafer is attached, the wafer ring is fixed in a region where the adhesive film 12 is not laminated.
  • the ultraviolet curable adhesive those having an ultraviolet curable functional group such as a carbon-carbon double bond and exhibiting adhesiveness can be used without particular limitation.
  • the ultraviolet curable pressure-sensitive adhesive include an additive-type ultraviolet curable pressure-sensitive adhesive in which an ultraviolet curable monomer component or an oligomer component is blended with a general pressure-sensitive adhesive such as the acrylic pressure-sensitive adhesive or the rubber-based pressure-sensitive adhesive. An agent can be illustrated.
  • UV curable monomer component to be blended examples include urethane oligomer, urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol.
  • examples include stall tetra (meth) acrylate, dipentaerystol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,4-butanediol di (meth) acrylate.
  • Examples of the ultraviolet curable oligomer component include urethane, polyether, polyester, polycarbonate, and polybutadiene oligomers, and those having a molecular weight in the range of about 100 to 30000 are suitable.
  • the blending amount of the ultraviolet curable monomer component and oligomer component can be appropriately determined in accordance with the type of the pressure-sensitive adhesive layer, and the amount capable of reducing the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer. In general, the amount is, for example, about 5 to 500 parts by weight, preferably about 40 to 150 parts by weight with respect to 100 parts by weight of the base polymer such as an acrylic polymer constituting the pressure-sensitive adhesive.
  • the UV-curable adhesive has a carbon-carbon double bond in the polymer side chain or main chain or at the main chain end as a base polymer.
  • Intrinsic ultraviolet curable pressure sensitive adhesives using Intrinsic UV curable adhesives do not need to contain oligomer components, which are low molecular weight components, or do not contain many, so they are stable without the oligomer components moving through the adhesive over time. It is preferable because an adhesive layer having a layered structure can be formed.
  • the base polymer having a carbon-carbon double bond those having a carbon-carbon double bond and having adhesiveness can be used without particular limitation.
  • those having an acrylic polymer as a basic skeleton are preferable.
  • the basic skeleton of the acrylic polymer include the acrylic polymers exemplified above.
  • the method for introducing the carbon-carbon double bond into the acrylic polymer is not particularly limited, and various methods can be adopted.
  • the carbon-carbon double bond can be easily introduced into the polymer side chain for easy molecular design.
  • a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is converted into an ultraviolet curable carbon-carbon double bond.
  • combinations of these functional groups include carboxylic acid groups and epoxy groups, carboxylic acid groups and aziridyl groups, hydroxyl groups and isocyanate groups, and the like.
  • a combination of a hydroxyl group and an isocyanate group is preferable because of easy tracking of the reaction.
  • the functional group may be on either side of the acrylic polymer and the compound as long as the combination of these functional groups generates an acrylic polymer having the carbon-carbon double bond.
  • it is preferable that the acrylic polymer has a hydroxyl group and the compound has an isocyanate group.
  • examples of the isocyanate compound having a carbon-carbon double bond include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, m-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, and the like.
  • the acrylic polymer a copolymer obtained by copolymerizing the above-exemplified hydroxy group-containing monomers, ether compounds of 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, or the like is used.
  • the base polymer (particularly acrylic polymer) having the carbon-carbon double bond can be used alone, but the ultraviolet curable monomer does not deteriorate the characteristics.
  • Components and oligomer components can also be blended.
  • the UV-curable oligomer component and the like are usually in the range of 30 parts by weight, preferably 0 to 10 parts by weight, with respect to 100 parts by weight of the base polymer.
  • the ultraviolet curable pressure-sensitive adhesive contains a photopolymerization initiator when cured by ultraviolet rays or the like.
  • the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone, 2-methyl-2-hydroxypropio ⁇ -ketol compounds such as phenone and 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- ( Acetophenone compounds such as methylthio) -phenyl] -2-morpholinopropane-1; benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether and anisoin methyl ether; ketal compounds such as benzyldimethyl ketal; 2-naphthalene
  • a compound that is colored by ultraviolet irradiation can be contained as necessary.
  • a compound to be colored in the pressure-sensitive adhesive layer 14 by irradiation with ultraviolet rays only the portion irradiated with ultraviolet rays can be colored. Thereby, it can be immediately determined by visual observation whether the adhesive layer 14 is irradiated with ultraviolet rays, the semiconductor wafer attachment portion can be easily recognized, and the semiconductor wafer can be easily attached.
  • the detection accuracy is increased, and no malfunction occurs when the semiconductor chip is picked up.
  • a compound colored by ultraviolet irradiation is a compound that is colorless or light-colored before ultraviolet irradiation but becomes colored by ultraviolet irradiation.
  • Preferable specific examples of such compounds include leuco dyes.
  • leuco dye conventional triphenylmethane, fluoran, phenothiazine, auramine, and spiropyran dyes are preferably used.
  • Developers preferably used together with these leuco dyes include conventionally used initial polymers of phenol formalin resins, aromatic carboxylic acid derivatives, electron acceptors such as activated clay, and further change the color tone. In some cases, various known color formers can be used in combination.
  • Such a compound colored by ultraviolet irradiation may be once dissolved in an organic solvent or the like and then contained in the ultraviolet curable pressure sensitive adhesive, or may be finely powdered and contained in the pressure sensitive adhesive.
  • the proportion of the compound used is desirably 10% by weight or less, preferably 0.01 to 10% by weight, more preferably 0.5 to 5% by weight in the pressure-sensitive adhesive layer 14. If the ratio of the compound exceeds 10% by weight, the ultraviolet ray irradiated to the pressure-sensitive adhesive layer 14 is excessively absorbed by the compound, so that the portion of the pressure-sensitive adhesive layer 14 corresponding to the semiconductor wafer attachment portion is not cured. It may be sufficient and the adhesive strength may not be sufficiently reduced. On the other hand, in order to sufficiently color, it is preferable that the ratio of the compound is 0.01% by weight or more.
  • the pressure-sensitive adhesive layer 14 is formed of an ultraviolet curable pressure-sensitive adhesive, all or a part of the base material 13 other than the part corresponding to the semiconductor wafer pasting part is shielded from light. It is possible to form the portion with reduced adhesive force by forming the ultraviolet curable pressure-sensitive adhesive layer 14 and then irradiating it with ultraviolet rays to cure the portion corresponding to the semiconductor wafer attachment portion.
  • a light shielding material what can become a photomask on a support film can be prepared by printing, vapor deposition, or the like. According to this manufacturing method, the film 10 for a semiconductor device of the present invention can be efficiently manufactured.
  • oxygen air
  • a method of covering the surface of the pressure-sensitive adhesive layer 14 with a separator, a method of irradiating ultraviolet rays in a nitrogen gas atmosphere, and the like can be mentioned.
  • the thickness of the pressure-sensitive adhesive layer 14 is preferably 1 to 50 ⁇ m, more preferably 2 to 30 ⁇ m, and still more preferably 5 to 5 ⁇ m from the viewpoint of compatibility between chip chipping surface chipping prevention and fixing and holding of the adhesive film. 25 ⁇ m.
  • the total thickness of the base material 13 and the pressure-sensitive adhesive layer 14, that is, the thickness Tb of the dicing film 11 is determined from the viewpoints of transportability, prevention of chip cut surface chipping, fixing and holding of the adhesive film, and pickup properties. From 25 to 180 ⁇ m, more preferably from 50 to 150 ⁇ m, still more preferably from 100 to 130 ⁇ m.
  • the adhesive film 12 is a layer having an adhesive function, and as a constituent material thereof, a thermoplastic resin and a thermosetting resin may be used in combination, or a thermoplastic resin may be used alone.
  • the tensile storage modulus at 23 ° C. before curing of the adhesive film 12 is preferably in the range of 50 to 5000 MPa, more preferably in the range of 300 to 4000 MPa, and even more preferably in the range of 500 to 3000 MPa.
  • the tensile storage modulus is preferably in the range of 50 to 5000 MPa, more preferably in the range of 300 to 4000 MPa, and even more preferably in the range of 500 to 3000 MPa.
  • the value of the tensile storage elastic modulus is based on the following measurement method. That is, the adhesive composition solution is applied onto a release liner that has been subjected to a mold release treatment and dried to form an adhesive film 12 having a thickness of 100 ⁇ m.
  • the adhesive film 12 is measured for a tensile storage elastic modulus at 23 ° C. before the adhesive film 12 is cured by using a viscoelasticity measuring device (Rheometrics: model: RSA-II). More specifically, the sample size is 30.0 ⁇ length 5.0 ⁇ thickness 0.1 mm, the measurement sample is set in a film tensile measurement jig, and the frequency is in the temperature range of ⁇ 30 ° C. to 280 ° C. The measurement is performed under the conditions of 10.0 Hz, a strain of 0.025%, and a heating rate of 10 ° C./min.
  • thermoplastic resin examples include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene resin, polycarbonate resin, heat Examples thereof include plastic polyimide resins, polyamide resins such as 6-nylon and 6,6-nylon, phenoxy resins, acrylic resins, saturated polyester resins such as PET and PBT, polyamideimide resins, and fluorine resins. These thermoplastic resins can be used alone or in combination of two or more. Of these thermoplastic resins, an acrylic resin that has few ionic impurities and high heat resistance and can ensure the reliability of the semiconductor device is particularly preferable.
  • the acrylic resin is not particularly limited, and includes one or more esters of acrylic acid or methacrylic acid ester having a linear or branched alkyl group having 30 or less carbon atoms, particularly 4 to 18 carbon atoms.
  • Examples include polymers as components.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an isobutyl group, an amyl group, an isoamyl group, a hexyl group, a heptyl group, a cyclohexyl group, and 2-ethylhexyl.
  • octyl group isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, lauryl group, tridecyl group, tetradecyl group, stearyl group, octadecyl group, or dodecyl group.
  • the other monomer forming the polymer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
  • Carboxyl group-containing monomers maleic anhydride or acid anhydride monomers such as itaconic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-methacrylic acid 4- Hydroxybutyl, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate or (4-hydroxymethylcyclohexyl) -Methyl Hydroxyl group-containing monomers such as acrylate, styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate or (meth) Examples thereof include sulfonic acid group-containing monomers such as
  • thermosetting resin examples include phenol resin, amino resin, unsaturated polyester resin, epoxy resin, polyurethane resin, silicone resin, and thermosetting polyimide resin. These resins can be used alone or in combination of two or more. In particular, an epoxy resin containing a small amount of ionic impurities that corrode semiconductor chips is preferable. Moreover, as a hardening
  • the epoxy resin is not particularly limited as long as it is generally used as an adhesive composition, for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type. , Biphenyl type, naphthalene type, fluorene type, phenol novolak type, orthocresol novolak type, trishydroxyphenylmethane type, tetraphenylolethane type, etc. Type or glycidylamine type epoxy resin is used. These can be used alone or in combination of two or more.
  • novolac type epoxy resins novolac type epoxy resins, biphenyl type epoxy resins, trishydroxyphenylmethane type resins or tetraphenylolethane type epoxy resins are particularly preferred. This is because these epoxy resins are rich in reactivity with a phenol resin as a curing agent and are excellent in heat resistance and the like.
  • the phenol resin acts as a curing agent for the epoxy resin.
  • examples include resol-type phenolic resins and polyoxystyrenes such as polyparaoxystyrene. These can be used alone or in combination of two or more. Of these phenol resins, phenol novolac resins and phenol aralkyl resins are particularly preferred. This is because the connection reliability of the semiconductor device can be improved.
  • the compounding ratio of the epoxy resin and the phenol resin is preferably such that, for example, the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents per equivalent of the epoxy group in the epoxy resin component. More preferred is 0.8 to 1.2 equivalents. That is, if the blending ratio of both is out of the above range, sufficient curing reaction does not proceed and the properties of the cured epoxy resin are likely to deteriorate.
  • the adhesive film 12 containing an epoxy resin, a phenol resin, and an acrylic resin is particularly preferable. Since these resins have few ionic impurities and high heat resistance, the reliability of the semiconductor chip can be ensured.
  • the mixing ratio of the epoxy resin and the phenol resin is 10 to 200 parts by weight with respect to 100 parts by weight of the acrylic resin component.
  • the adhesive film 12 according to the present embodiment is crosslinked to some extent in advance, a polyfunctional compound that reacts with a functional group at the molecular chain end of the polymer may be added as a crosslinking agent during production. . Thereby, the adhesive property under high temperature is improved and heat resistance is improved.
  • crosslinking agent conventionally known crosslinking agents can be used. Particularly preferred are polyisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, adducts of polyhydric alcohol and diisocyanate.
  • the addition amount of the crosslinking agent is usually preferably 0.05 to 7 parts by weight with respect to 100 parts by weight of the polymer. When the amount of the cross-linking agent is more than 7 parts by weight, the adhesive force is lowered, which is not preferable. On the other hand, if it is less than 0.05 parts by weight, the cohesive force is insufficient, which is not preferable. Moreover, you may make it include other polyfunctional compounds, such as an epoxy resin, together with such a polyisocyanate compound as needed.
  • an inorganic filler can be appropriately blended into the adhesive film 12 according to its use.
  • the blending of the inorganic filler makes it possible to impart conductivity, improve thermal conductivity, adjust the elastic modulus, and the like.
  • the inorganic filler include silica, clay, gypsum, calcium carbonate, barium sulfate, alumina oxide, beryllium oxide, silicon carbide, silicon nitride and other ceramics, aluminum, copper, silver, gold, nickel, chromium, bell
  • silica particularly a melting strength is preferably used.
  • the average particle size of the inorganic filler is preferably in the range of 0.01 to 80 ⁇ m.
  • the blending amount of the inorganic filler is preferably set to 0 to 80 parts by weight, more preferably 0 to 70 parts by weight with respect to 100 parts by weight of the organic component.
  • the adhesive film 12 can be appropriately mixed with other additives as necessary.
  • other additives include flame retardants, silane coupling agents, ion trapping agents, and the like.
  • flame retardant include antimony trioxide, antimony pentoxide, brominated epoxy resin, and the like. These can be used alone or in combination of two or more.
  • silane coupling agent include ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and the like. These compounds can be used alone or in combination of two or more.
  • the ion trapping agent include hydrotalcites and bismuth hydroxide. These can be used alone or in combination of two or more.
  • the thickness of the adhesive film 12 is not particularly limited, but is, for example, about 5 to 100 ⁇ m, preferably about 5 to 70 ⁇ m.
  • the film for semiconductor device 10 can have antistatic ability. As a result, it is possible to prevent the circuit from being broken due to the generation of static electricity during the bonding and peeling, and the resulting charging of the semiconductor wafer or the like.
  • the antistatic ability is imparted by adding an antistatic agent or a conductive material to the base material 13, the pressure-sensitive adhesive layer 14 or the adhesive film 12, and providing a conductive layer made of a charge transfer complex or a metal film on the base material 13. Etc., etc. As these methods, a method in which impurity ions that may change the quality of the semiconductor wafer are less likely to be generated is preferable.
  • a conductive substance (conductive filler) blended for the purpose of imparting conductivity and improving thermal conductivity spherical, needle-like, and flaky shapes such as silver, aluminum, gold, copper, nickel, and conductive alloys
  • spherical, needle-like, and flaky shapes such as silver, aluminum, gold, copper, nickel, and conductive alloys
  • metal powders, metal oxides such as alumina, amorphous carbon black, and graphite examples thereof include metal powders, metal oxides such as alumina, amorphous carbon black, and graphite.
  • the adhesive film 12 is non-conductive because it can be prevented from electrically leaking.
  • the adhesive film 12 is protected by the cover film 2.
  • the cover film 2 has a function as a protective material that protects the adhesive film 12 until it is put into practical use.
  • the cover film 2 is peeled off when a semiconductor wafer is stuck on the adhesive film 12 of the adhesive film with a dicing sheet.
  • a plastic film or paper surface-coated with a release agent such as polyethylene terephthalate (PET), polyethylene, polypropylene, a fluorine-type release agent, or a long-chain alkyl acrylate-type release agent can be used.
  • the thickness Ta of the cover film 2 is preferably 10 to 100 ⁇ m, more preferably 15 to 75 ⁇ m, and further preferably 25 to 50 ⁇ m from the viewpoint of workability and transportability.
  • the adhesive layer 14 is formed on the substrate 13 to form the dicing film 11, and the adhesive film 12 is formed on the substrate separator 22.
  • the base material 13 can be formed by a conventionally known film forming method.
  • the film forming method include a calendar film forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T-die extrusion method, a co-extrusion method, and a dry lamination method.
  • the coating film is dried under predetermined conditions (heat-crosslinked as necessary) to form a pressure-sensitive adhesive layer 14.
  • predetermined conditions heat-crosslinked as necessary
  • the drying conditions can be appropriately set according to the thickness and material of the coating film. Specifically, for example, the drying temperature is 80 to 150 ° C. and the drying time is 0.5 to 5 minutes.
  • the coating film may be dried on the said drying conditions, and the adhesive layer 14 may be formed.
  • the produced dicing film 11 may have a long form wound in a roll shape. In this case, it is preferable to wind the dicing film 11 while applying a tensile tension in the longitudinal direction or the width direction so that no slack, winding deviation, or positional deviation occurs. However, by applying a tensile tension, the dicing film 11 is wound into a roll shape with a residual tensile strain remaining. In addition, although the dicing film 11 may be extended
  • the pressure-sensitive adhesive layer 14 is made of an ultraviolet-curing pressure-sensitive adhesive and is pre-cured with ultraviolet light, it is formed as follows. That is, after an ultraviolet curable pressure-sensitive adhesive composition is applied onto the substrate 13 to form a coating film, the coating film is dried under a predetermined condition (heat-crosslinked as necessary) to form a pressure-sensitive adhesive layer. Form.
  • the coating method, coating conditions, and drying conditions can be performed in the same manner as described above.
  • an ultraviolet curable pressure-sensitive adhesive composition may be applied onto the first separator 21 to form a coating film, and then the coating film may be dried under the drying conditions to form a pressure-sensitive adhesive layer. Thereafter, the pressure-sensitive adhesive layer is transferred onto the substrate 13.
  • the adhesive layer is irradiated with ultraviolet rays under predetermined conditions.
  • the ultraviolet irradiation condition is not particularly limited, it is usually preferably in the range where the integrated light quantity is 50 to 800 mJ / cm 2, more preferably in the range of 100 to 500 mJ / cm 2.
  • the peeling force F2 between the adhesive film 12 and the dicing film 11 can be controlled within a range of 0.08 to 10 N / 100 mm. If the irradiation with ultraviolet rays is less than 30 mJ / cm 2, the pressure-sensitive adhesive layer 14 may be insufficiently cured, and the peeling force from the adhesive film 12 may be excessively increased.
  • the adhesion with the die bond film is increased, resulting in a decrease in pick-up property. Further, adhesive residue may occur on the adhesive film after pickup.
  • the integrated light quantity exceeds 1000 mJ / cm 2
  • the peeling force from the adhesive film 12 may be too small.
  • interface peeling may occur between the pressure-sensitive adhesive layer 14 and the adhesive film 12.
  • chip skipping may occur during dicing of the semiconductor wafer.
  • the base material 13 may be thermally damaged.
  • the curing of the pressure-sensitive adhesive layer 14 proceeds excessively, the tensile elastic modulus becomes too large, and the expandability decreases.
  • the ultraviolet irradiation is preferably performed from the substrate 13 side.
  • the production process of the adhesive film 12 is performed as follows. That is, an adhesive composition solution for forming the adhesive film 12 is applied on the base separator 22 so as to have a predetermined thickness, thereby forming a coating film. Thereafter, the coating film is dried under predetermined conditions to form the adhesive film 12. It does not specifically limit as a coating method, For example, roll coating, screen coating, gravure coating, etc. are mentioned. Further, the drying conditions can be appropriately set according to the thickness and material of the coating film. Specifically, for example, the drying is performed within a range of 70 to 160 ° C. and a drying time of 1 to 5 minutes.
  • the coating film may be dried on the said drying conditions, and the adhesive film 12 may be formed. Thereafter, the adhesive film 12 is bonded together with the second separator 23 on the substrate separator 22. Thereby, the laminated
  • This laminated film may have a long form wound in a roll shape. In this case, it is preferable to wind the adhesive film 12 while applying a tensile tension in the longitudinal direction or the width direction so that the adhesive film 12 is not loosened, wound or misaligned.
  • the adhesive film 12 is punched in accordance with the shape of the semiconductor wafer to be attached, and is attached to the dicing film 11.
  • the adhesive film 1 with a dicing sheet is obtained. That is, the first separator 21 is peeled off from the dicing film 11 and the second separator 23 is peeled off from the punched adhesive film 12 so that the adhesive film 12 and the pressure-sensitive adhesive layer 14 are bonded to each other. Paste together (see FIG. 3C).
  • pressure bonding is performed on at least one of the dicing film 11 and the adhesive film 12 while applying a tensile tension to the peripheral edge.
  • a tensile tension may be applied within a range of 10 to 25 N from the viewpoint of preventing the dicing film 11 from being loosened, wound, misaligned, or voids (bubbles). Within this range, even if tensile residual strain remains in the dicing film 11, it is possible to prevent the occurrence of interface peeling between the dicing film 11 and the adhesive film 12.
  • the dicing film 11 and the adhesive film 12 can be bonded together by, for example, pressure bonding.
  • the laminating temperature is not particularly limited, but is usually preferably 30 to 80 ° C, more preferably 30 to 60 ° C, and particularly preferably 30 to 50 ° C.
  • the linear pressure is not particularly limited, but is usually preferably 0.1 to 20 kgf / cm, and more preferably 1 to 10 kgf / cm.
  • the peeling force F2 between the adhesive film 12 and the dicing film 11 can be controlled within the range of 0.08 to 10 N / 100 mm.
  • the peeling force F2 between the dicing film 11 and the adhesive film 12 can be increased by increasing the laminating temperature within the above range.
  • the peeling force F2 can be increased by increasing the linear pressure within the above range.
  • the base material separator 22 on the adhesive film 12 is peeled off, and the cover film 2 is bonded while applying tensile tension.
  • the dicing film 11 is punched out into a circular shape corresponding to the ring frame at a predetermined interval. Thereby, the film 10 for semiconductor devices by which the pre-cut adhesive film 1 with a dicing sheet was laminated
  • the bonding of the adhesive film 12 to the cover film 2 in the adhesive film 1 with a dicing sheet is preferably performed by pressure bonding.
  • the lamination temperature is not particularly limited, but is usually preferably 20 to 80 ° C., more preferably 20 to 60 ° C., and particularly preferably 20 to 50 ° C.
  • the linear pressure is not particularly limited, but is usually preferably 0.1 to 20 kgf / cm, more preferably 0.2 to 10 kgf / cm.
  • the laminating temperature and / or the linear pressure are adjusted within the above numerical ranges, respectively, and bonded to the cover film 2
  • the peeling force F1 between the adhesive film 12 and the cover film 2 can be controlled within the range of 0.025 to 0.075 N / 100 mm.
  • the peeling force F1 between the adhesive film with dicing sheet 1 and the cover film 2 can be increased by increasing the laminating temperature within the above range.
  • the peeling force F1 can be increased by increasing the linear pressure within the above range.
  • a tensile tension may be applied within a range of 10 to 25N. If it is in the said range, even if the tensile residual distortion remains in the cover film 2, it can prevent that the film floating phenomenon of the cover film 2 with respect to the adhesive film 1 with a dicing sheet generate
  • the first separator 21 bonded on the pressure-sensitive adhesive layer 14 of the dicing film 11, the substrate separator 22 of the adhesive film 12, and the second separator 23 bonded on the adhesive film 12 are not particularly limited.
  • a conventionally known release-treated film can be used.
  • the first separator 21 and the second separator 23 each have a function as a protective material.
  • the substrate separator 22 has a function as a substrate when the adhesive film 12 is transferred onto the pressure-sensitive adhesive layer 14 of the dicing film 11.
  • the material constituting each of these films is not particularly limited, and conventionally known materials can be employed.
  • PET polyethylene terephthalate
  • polyethylene polyethylene
  • polypropylene polypropylene
  • a plastic film or paper surface-coated with a release agent such as a fluorine-type release agent or a long-chain alkyl acrylate release agent
  • a release agent such as a fluorine-type release agent or a long-chain alkyl acrylate release agent
  • the adhesive film of the present invention can be used as a die bond film or a flip chip type semiconductor back film.
  • the flip chip type semiconductor back film is used for forming on the back surface of a semiconductor element (for example, a semiconductor chip) flip-chip connected to an adherend (for example, various substrates such as a lead frame and a circuit board). Is.
  • Example 1 ⁇ Production of dicing film>
  • 2EHA 2-ethylhexyl acrylate
  • HOA 2-hydroxyethyl acrylate
  • 11.2 parts, 0.2 part of benzoyl peroxide and 65 parts of toluene were added and polymerized in a nitrogen stream at 61 ° C. for 6 hours to obtain an acrylic polymer A having a weight average molecular weight of 850,000. It was.
  • the molar ratio of 2EHA to HEA was 100 mol to 20 mol.
  • the weight average molecular weight was measured by GPC (gel permeation chromatography), and was a value calculated by polystyrene conversion.
  • the pressure-sensitive adhesive solution prepared above was applied onto the surface of the PET release liner (first separator) that had been subjected to the silicone treatment, and heat-crosslinked at 120 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 10 ⁇ m.
  • a polyolefin film (base material) having a thickness of 100 ⁇ m was bonded to the surface of the pressure-sensitive adhesive layer. Thereafter, it was stored at 50 ° C. for 24 hours.
  • the PET release liner was peeled off, and ultraviolet rays were directly irradiated only to the portion (circular shape with a diameter of 220 mm) corresponding to the adhesive layer of the semiconductor wafer (circular shape with a diameter of 200 mm).
  • the irradiation conditions are as follows. Further, when the tensile elastic modulus of the pressure-sensitive adhesive layer was measured by a method described later, the tensile elastic modulus was 19.7 MPa.
  • UV irradiation device high-pressure mercury lamp UV irradiation integrated light quantity: 500 mJ / cm2 Output: 120W Irradiation intensity: 200 mW / cm 2
  • Isocyanate-based crosslinking agent (Nippon Polyurethane) for 100 parts of acrylic acid ester-based polymer (manufactured by Negami Kogyo Co., Ltd., trade name: Paracron W-197CM, Tg: 18 ° C.) mainly composed of ethyl acrylate-methyl methacrylate.
  • This adhesive composition solution is applied onto a release-treated film (base separator) with a fountain coater to form a coating layer, and hot air at 150 ° C. and 10 m / s is directly applied to the coating layer for 2 minutes. Sprayed and dried. Thus, an adhesive film having a thickness of 25 ⁇ m was produced on the release treatment film.
  • a release treatment film (base separator) a polyethylene terephthalate film (thickness 50 ⁇ m) subjected to silicone release treatment was used.
  • the adhesive film was cut into a circular shape having a diameter of 230 mm, and the pressure-sensitive adhesive layer of the dicing film and the adhesive film cut into a circular shape were bonded together.
  • a nip roll is used for the bonding, and the bonding conditions are a lamination temperature of 50 ° C. and a linear pressure of 3 kgf / cm.
  • the substrate separator on the adhesive film is peeled off, and a release treatment film (cover film) is used as silicone.
  • a release-treated polyethylene terephthalate film was bonded. At this time, in order to prevent misalignment, voids (bubbles), etc.
  • a linear pressure is applied without applying a lamination temperature while applying a tensile tension of 17 N in the MD direction using a dancer roll. Bonding was performed at 2 kgf / cm to prepare an adhesive film with a dicing sheet.
  • Example 2 ⁇ Production of dicing film>
  • the dicing film according to this example was the same as that used in Example 1.
  • An isocyanate-based crosslinking agent (Nippon Polyurethane) for 100 parts of an acrylic acid ester-based polymer (manufactured by Negami Kogyo Co., Ltd., trade name: Paracron W-197C, Tg: 18 ° C.) mainly composed of ethyl acrylate-methyl methacrylate.
  • the film for a semiconductor device according to Example 2 was obtained by bonding a polyethylene terephthalate film (thickness 38 ⁇ m) subjected to silicone release treatment in the same manner as Example 1 except that the adhesive film was used. A film was prepared.
  • Example 3 ⁇ Production of dicing film>
  • the dicing film according to this example is the above except that the thickness of the pressure-sensitive adhesive layer after drying is 5 ⁇ m, the thickness of the polyolefin film (base material) to be used is 40 ⁇ m, and the total thickness of the dicing film is 45 ⁇ m.
  • a dicing film according to this example was produced in the same manner as in Example 1.
  • a film for a semiconductor device according to Example 3 was obtained by laminating a polyethylene terephthalate film (thickness: 100 ⁇ m) subjected to silicone release treatment in the same manner as in Example 1 except that the dicing film was used. A film was prepared.
  • Example 4 ⁇ Production of dicing film>
  • the dicing film according to this example is the above except that the thickness of the pressure-sensitive adhesive layer after drying is 10 ⁇ m, the thickness of the polyolefin film (base material) to be used is 150 ⁇ m, and the total thickness of the dicing film is 160 ⁇ m.
  • a dicing film according to this example was produced in the same manner as in Example 1.
  • the film for a semiconductor device according to Example 4 was obtained by laminating a polyethylene terephthalate film (thickness: 12 ⁇ m) subjected to silicone release treatment in the same manner as in Example 1 except that the dicing film was used. A film was prepared.
  • Example 5 ⁇ Production of dicing film>
  • the dicing film according to this example is the above except that the thickness of the pressure-sensitive adhesive layer after drying is 5 ⁇ m, the thickness of the polyolefin film (base material) to be used is 75 ⁇ m, and the total thickness of the dicing film is 80 ⁇ m.
  • a dicing film according to this example was produced in the same manner as in Example 1.
  • the film for a semiconductor device according to Example 5 was a polyethylene terephthalate that was subjected to silicone release treatment in the same manner as in Example 1 except that the dicing film was used, the lamination temperature was 50 ° C., and the linear pressure was 5 kg / cm.
  • a film for manufacturing a semiconductor device was produced by laminating a film (thickness: 75 ⁇ m).
  • the dicing film according to this comparative example is the above except that the thickness of the pressure-sensitive adhesive layer after drying is 50 ⁇ m, the thickness of the polyolefin film (base material) to be used is 150 ⁇ m, and the total thickness of the dicing film is 200 ⁇ m.
  • a dicing film according to this comparative example was produced in the same manner as in Example 1.
  • the film for a semiconductor device according to Comparative Example 1 uses the dicing film, polyethylene terephthalate subjected to silicone release treatment in the same manner as in Example 1 except that the laminating temperature is set to 60 ° C. and the linear pressure is set to 5 kg / cm.
  • a film for a semiconductor device was produced by laminating a film (thickness: 12 ⁇ m).
  • the dicing film according to this comparative example is the above except that the thickness of the pressure-sensitive adhesive layer after drying is 15 ⁇ m, the thickness of the polyolefin film (base material) to be used is 40 ⁇ m, and the total thickness of the dicing film is 55 ⁇ m.
  • a dicing film according to this comparative example was produced in the same manner as in Example 1.
  • the film for a semiconductor device according to Comparative Example 2 is a semiconductor device obtained by laminating a polyethylene terephthalate film (thickness 150 ⁇ m) subjected to silicone release treatment in the same manner as in Example 1 except that the dicing film is used. A film was prepared.
  • the peeling force was measured by a T-type peeling test (JIS K6854-3) under the conditions of a temperature of 23 ⁇ 2 ° C., a relative humidity of 55 ⁇ 5% Rh, and a peeling speed of 300 mm / min.
  • a tensile tester a trade name “Autograph AGS-H” (manufactured by Shimadzu Corporation) was used.
  • the value of the tensile elastic modulus of the pressure-sensitive adhesive layer is determined by the following measurement method. That is, a sample having a length of 30.0 mm, a width of 10.0 mm, and a cross-sectional area of 0.1 to 0.5 mm 2 is cut out from the adhesive layer 14. The sample was subjected to a tensile test in the MD direction at a measurement temperature of 23 ° C., a distance between chucks of 20 mm, and a tensile speed of 50 mm / min, and the amount of change (mm) due to the extension of the sample was measured.
  • the adhesive compositions in Examples and Comparative Examples were applied on a release liner subjected to a release treatment so as to have a thickness of 100 ⁇ m to obtain a dicing film.
  • the tensile elasticity modulus in 23 degreeC was measured using the viscoelasticity measuring apparatus (Rheometrics company_made: type
  • the presence or absence of voids in the film for a semiconductor device obtained in each example and comparative example was confirmed as follows. That is, the cover film was peeled off from each semiconductor device film, and the semiconductor wafer was mounted on the adhesive film. A semiconductor wafer having a size of 8 inches and a thickness of 75 ⁇ m was used. The mounting conditions of the semiconductor wafer were as follows.
  • Pasting device ACC Co., Ltd., trade name: RM-300 Pasting speed meter: 50 mm / sec Pasting pressure: 0.2 MPa Pasting temperature: 50 ° C
  • the cover film was peeled off from each film for a semiconductor device, and a semiconductor wafer was mounted on the adhesive film.
  • a semiconductor wafer having a size of 8 inches and a thickness of 75 ⁇ m was used.
  • the semiconductor wafer mounting conditions were the same as described above.
  • the semiconductor wafer was diced according to the following conditions to form 30 semiconductor chips. Furthermore, the semiconductor chip was picked up together with the adhesive film. The pick-up was performed on 30 semiconductor chips (10 mm long ⁇ 10 mm wide), and the success rate was calculated by counting the cases where the semiconductor chip was successfully picked up without breakage. The results are shown in Table 1 below. In Comparative Example 1, the cover film and the adhesive film were not peeled off during the pasting with the mounter, and a transport error (cannot be printed) occurred several times. The pickup conditions are as follows. *
  • Dicing conditions Dicing method: Step cut Dicing device: DISCO DFD6361 (trade name, manufactured by DISCO Corporation) Dicing speed: 30mm / sec Dicing blade: Z1; “NBC-ZH203O-SE27HCD” manufactured by Disco Corporation Z2: “NBC-ZH103O-SE27HCB” manufactured by Disco Corporation Dicing blade rotation speed: Z1; 40,000 rpm, Z2; 45,000 rpm Dicing tape cutting depth: 20 ⁇ m Wafer chip size: 10mm x 10mm
  • the peel force F1 represents the peel force between the adhesive film with the dicing sheet and the cover film
  • the peel force F2 represents the peel force between the dicing film and the adhesive film
  • the peel force F3 represents the cover. It represents the peeling force between the film and the dicing film (adhesive layer).
  • the cover film was not peeled off from the film for a semiconductor device, and a transport error occurred several times. Further, chip skipping and chipping occurred during dicing of the semiconductor wafer. Further, in the film for a semiconductor device of Comparative Example 2, the pick-up property was good, but voids were confirmed immediately after mounting the semiconductor wafer. In addition, when the sample was wound and stored refrigerated for one month, voids due to transfer of traces were confirmed. Moreover, the phenomenon of the film lift of the cover film was also confirmed.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)
  • Container, Conveyance, Adherence, Positioning, Of Wafer (AREA)
  • Laminated Bodies (AREA)
  • Die Bonding (AREA)

Abstract

L'invention concerne un film pour dispositif à semi-conducteurs, sur lequel un film de découpage de dés qui est un film adhésif stratifié sur la partie supérieure d'un film de découpage de dés, est stratifié sur un film de revêtement à des intervalles prédéfinis. Le film pour dispositif à semi-conducteurs peut empêcher la formation de marques de transfert sur le film adhésif lorsqu'il est enroulé autour d'un cylindre. Le film pour dispositif à semi-conducteurs de l'invention est un film sur lequel le film adhésif doté d'une feuille de découpage qui est le film adhésif stratifié sur la partie supérieure du film de découpage en dés, est stratifié sur le film de revêtement à des intervalles prédéfinis, et présente un rapport Ta/Tb entre l'épaisseur de film de revêtement (Ta) et l'épaisseur du film de découpage de dés (Tb) compris entre 0,07 et 2.5.
PCT/JP2011/069473 2010-09-06 2011-08-29 Film pour dispositif à semi-conducteurs et dispositif à semi-conducteurs Ceased WO2012032959A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201180042794.2A CN103081068B (zh) 2010-09-06 2011-08-29 半导体装置用薄膜以及半导体装置
KR1020117027458A KR101190467B1 (ko) 2010-09-06 2011-08-29 반도체 장치용 필름 및 반도체 장치

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JP2010199028A JP4991921B2 (ja) 2010-09-06 2010-09-06 半導体装置用フィルム、及び、半導体装置
JP2010-199028 2010-09-06

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WO2012032959A1 true WO2012032959A1 (fr) 2012-03-15

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JP6297786B2 (ja) * 2012-12-10 2018-03-20 日東電工株式会社 接着シート、ダイシングテープ一体型接着シート、半導体装置の製造方法、及び、半導体装置
JP2014216488A (ja) * 2013-04-25 2014-11-17 日東電工株式会社 接着フィルム、ダイシング・ダイボンドフィルム、半導体装置の製造方法及び半導体装置
JP5799180B1 (ja) * 2013-11-19 2015-10-21 積水化学工業株式会社 半導体接合用接着フィルム
US10510578B2 (en) 2014-03-24 2019-12-17 Lintec Corporation Protective film forming film, protective film forming sheet and work product manufacturing method
JP2016111156A (ja) * 2014-12-04 2016-06-20 古河電気工業株式会社 ウェハ加工用テープ
JP6406999B2 (ja) * 2014-12-04 2018-10-17 古河電気工業株式会社 ウェハ加工用テープ
JP6382088B2 (ja) * 2014-12-04 2018-08-29 古河電気工業株式会社 ウェハ加工用テープ
JP2016111158A (ja) * 2014-12-04 2016-06-20 古河電気工業株式会社 ウェハ加工用テープ
JP2017183705A (ja) * 2016-03-24 2017-10-05 日東電工株式会社 ダイシングダイボンドフィルム、及び、半導体装置の製造方法
JP2018019022A (ja) * 2016-07-29 2018-02-01 日東電工株式会社 ダイシングテープ一体型半導体裏面用フィルム、及び、半導体装置の製造方法
CN106514014B (zh) * 2017-01-17 2018-06-15 京东方科技集团股份有限公司 一种基板的激光修复方法及其激光修复系统
JP6389537B2 (ja) * 2017-01-19 2018-09-12 日東電工株式会社 半導体装置の製造に用いられる接着シート、ダイシングテープ一体型接着シート、半導体装置、及び、半導体装置の製造方法
JP7256618B2 (ja) * 2018-08-29 2023-04-12 タツタ電線株式会社 転写フィルム付電磁波シールドフィルム、転写フィルム付電磁波シールドフィルムの製造方法及びシールドプリント配線板の製造方法
JP2022044992A (ja) * 2020-09-08 2022-03-18 昭和電工マテリアルズ株式会社 フィルム状接着剤、接着シート、並びに半導体装置及びその製造方法
JP7668131B2 (ja) * 2021-03-04 2025-04-24 リンテック株式会社 ワーク加工用シート
CN116442094A (zh) * 2023-03-24 2023-07-18 中国电子科技集团公司第二十九研究所 一种用于微小电路片的砂轮切割方法

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JP2009027054A (ja) * 2007-07-23 2009-02-05 Lintec Corp 半導体装置の製造方法
WO2009099191A1 (fr) * 2008-02-07 2009-08-13 Sumitomo Bakelite Company Limited Film pour semi-conducteur, procédé de fabrication de dispositif à semi-conducteur et dispositif à semi-conducteur
JP2009212511A (ja) * 2008-02-07 2009-09-17 Sumitomo Bakelite Co Ltd ダイシングシート機能付き半導体用フィルムおよび半導体装置
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JP2012059769A (ja) 2012-03-22
KR20120034619A (ko) 2012-04-12
KR101190467B1 (ko) 2012-10-11
TWI458005B (zh) 2014-10-21
TW201218264A (en) 2012-05-01
JP4991921B2 (ja) 2012-08-08
CN103081068B (zh) 2016-08-03

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