WO2016093308A1 - Dicing sheet, dicing/die-bonding film, and method for manufacturing semiconductor device - Google Patents
Dicing sheet, dicing/die-bonding film, and method for manufacturing semiconductor device Download PDFInfo
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- WO2016093308A1 WO2016093308A1 PCT/JP2015/084644 JP2015084644W WO2016093308A1 WO 2016093308 A1 WO2016093308 A1 WO 2016093308A1 JP 2015084644 W JP2015084644 W JP 2015084644W WO 2016093308 A1 WO2016093308 A1 WO 2016093308A1
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- WIPO (PCT)
- Prior art keywords
- adhesive layer
- dicing
- film
- die
- dicing sheet
- Prior art date
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
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- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 description 1
- IUURMAINMLIZMX-UHFFFAOYSA-N tris(2-nonylphenyl)phosphane Chemical compound CCCCCCCCCC1=CC=CC=C1P(C=1C(=CC=CC=1)CCCCCCCCC)C1=CC=CC=C1CCCCCCCCC IUURMAINMLIZMX-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/27—Manufacturing methods
-
- 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
-
- 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
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
-
- 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
- H01L2224/27—Manufacturing methods
- H01L2224/274—Manufacturing methods by blanket deposition of the material of the layer connector
- H01L2224/2743—Manufacturing methods by blanket deposition of the material of the layer connector in solid form
- H01L2224/27436—Lamination of a preform, e.g. foil, sheet or layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/8319—Arrangement of the layer connectors prior to mounting
- H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
Definitions
- the present invention relates to a dicing sheet, a dicing die-bonding film, and a method for manufacturing a semiconductor device.
- a dicing die bond having a base material 911 and a dicing sheet 901 having an adhesive layer 912 disposed on the base material 911 and an adhesive layer 903 disposed on the adhesive layer 912.
- the wafer 904 having the semiconductor elements 905A, 905B, 905C,..., 905H and the modified region 941 to the adhesive layer 903 and expanding the dicing sheet 901, A method of dividing the wafer 904 and the adhesive layer 903 starting from the modified region 941 is known (see, for example, Patent Documents 1 and 2).
- the peripheral portion 912b sags after the expansion is solved. If the slack in the peripheral portion 912b is left unattended, the semiconductor elements 905A and 905B, the semiconductor elements 905B and 905C,..., May contact the semiconductor elements 905G and 905H.
- An object of the present invention is to provide a dicing sheet that can solve the above-described problems and remove sagging and prevent contact between semiconductor elements.
- the present invention relates to a dicing sheet that shrinks when heated at 100 ° C. for 1 minute, and whose second length in the MD direction after heating is 95% or less with respect to the first length in the MD direction before heating of 100%. . Since the second length is 95% or less with respect to the first length of 100%, sagging can be removed by heating, and contact between the semiconductor elements can be prevented.
- the dicing sheet of the present invention preferably has the following properties. That is, the tensile stress when stretched by 3% in the MD direction at 23 ° C. is 1 N / mm 2 or more. When it is 1 N / mm 2 or more, an appropriate tensile stress is applied at the time of cleaving the semiconductor wafer, so that the semiconductor wafer can be cleaved and the semiconductor elements can be spaced apart.
- the dicing sheet of the present invention preferably has the following properties. That is, the tensile stress when stretched 6% in the MD direction at 23 ° C. is 1.5 N / mm 2 or more. When it is 1.5 N / mm 2 or more, an appropriate tensile stress is applied at the time of cleaving the semiconductor wafer, so that the semiconductor wafer can be cleaved and the semiconductor elements can be spaced apart.
- the thickness of the dicing sheet of the present invention is preferably 40 ⁇ m to 200 ⁇ m.
- the dicing sheet of the present invention usually comprises a base material and an adhesive layer disposed on the base material.
- the present invention also relates to a dicing die-bonding film comprising a dicing sheet and an adhesive layer disposed on the pressure-sensitive adhesive layer.
- the glass transition temperature of the adhesive layer is preferably 0 ° C. or higher.
- the pressure-sensitive adhesive layer includes a central portion in contact with the adhesive layer and a peripheral portion disposed around the central portion.
- the present invention also includes a step of preparing the divided body, a step of dividing the divided wafer and the adhesive layer from the modified region by expanding the dicing sheet, and a step of dividing the divided wafer and the adhesive layer. And a step of heating a peripheral portion later.
- the divided body includes a dicing die-bonding film and a divided wafer disposed on the adhesive layer.
- the divided wafer has a modified region.
- the dicing sheet 1 includes a base material 11 and an adhesive layer 12 arranged on the base material 11.
- Dicing sheet 1 has the following properties. That is, it shrinks by heating at 100 ° C. for 1 minute, and the second length in the MD direction after heating is 95% or less with respect to the first length 100% in the MD (Machine Direction) direction before heating.
- the second length is preferably 96% or less with respect to the first length of 100%.
- the second length is, for example, 50% or more with respect to the first length of 100%.
- the value of the ratio of the second length to the first length can be controlled by the material of the base material 11 and the film forming method of the base material 11. Especially, the influence which the film forming method of the base material 11 has on the value of the ratio of the second length to the first length is great. For example, by stretching the substrate 11, the value of the ratio of the second length to the first length can be reduced.
- the dicing sheet 1 preferably has the following properties. That is, the tensile stress when stretched by 3% in the MD direction at 23 ° C. is preferably 1 N / mm 2 or more. When it is 1 N / mm 2 or more, an appropriate tensile stress is applied at the time of cleaving the semiconductor wafer, so that the semiconductor wafer can be cleaved and the semiconductor elements can be spaced apart. In addition, the distance between the semiconductor elements can be maintained.
- the upper limit of the tensile stress when extending 3% in the MD direction at 23 ° C. is, for example, 15 N / mm 2 .
- the dicing sheet 1 preferably has the following properties. That is, the tensile stress when stretched 6% in the MD direction at 23 ° C. is preferably 1.5 N / mm 2 or more. When it is 1.5 N / mm 2 or more, an appropriate tensile stress is applied at the time of cleaving the semiconductor wafer, so that the semiconductor wafer can be cleaved and the semiconductor elements can be spaced apart. In addition, the distance between the semiconductor elements can be maintained.
- the upper limit of the tensile stress when extending 6% in the MD direction at 23 ° C. is, for example, 20 N / mm 2 .
- the thickness of the dicing sheet 1 is preferably 40 ⁇ m or more, more preferably 60 ⁇ m or more. On the other hand, the thickness of the dicing sheet 1 is preferably 200 ⁇ m or less, more preferably 180 ⁇ m or less.
- the thickness of the substrate 11 is preferably 50% or more, more preferably 70% or more.
- the thickness of the base material 11 is preferably 98% or less, more preferably 95% or less.
- the substrate 11 examples include a polyethylene terephthalate film, a polyethylene film, a polystyrene film, a polypropylene film, a polyamide film, a polyurethane film, a polyvinylidene chloride film, a polyvinyl chloride film, an ethylene vinyl acetate copolymer film, and an ethylene-acrylic ester.
- a copolymer film, a polyvinyl chloride film, etc. are mentioned.
- an unstretched film As the substrate 11, an unstretched film, a uniaxially stretched film, a biaxially stretched film, or the like can be used. Among these, an unstretched film is preferable because it has no anisotropy.
- the structure of the base material 11 includes a single layer, a multilayer, and the like.
- the surface of the base material 11 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 pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer 12 is not particularly limited, and for example, a general pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive can be used.
- a general pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive
- acrylic adhesives based on acrylic polymers are used as the base polymer from the standpoint of cleanability of electronic components that are difficult to contaminate such as semiconductor wafers and glass with organic solvents such as ultrapure water and alcohol. preferable.
- 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, Pentyl 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, Straight chain or branched chain alkyl esters having 1 to 30 carbon atoms, particularly 4 to 18 carbon atoms, such as octadecyl ester and ei
- 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. May be.
- 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; Sti Contains sulfonic acid groups such as ethylene sulfonic acid, allyl s
- 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
- 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 carried out by any method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like. From the viewpoint of preventing contamination of a clean adherend, it is preferable that the content of the low molecular weight substance is small. From this point, 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, or a melamine crosslinking agent and reacting them.
- a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, or 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 various conventionally known tackifiers and anti-aging agents may be used for the pressure-sensitive adhesive, if necessary,
- the pressure-sensitive adhesive layer 12 can be formed of a radiation curable pressure-sensitive adhesive.
- the radiation curable pressure-sensitive adhesive can easily reduce its adhesive strength by increasing the degree of crosslinking by irradiation with radiation such as ultraviolet rays.
- the radiation curable pressure-sensitive adhesive those having a radiation curable functional group such as a carbon-carbon double bond and exhibiting adhesiveness can be used without particular limitation.
- the radiation curable pressure-sensitive adhesive include an addition-type radiation curable pressure-sensitive adhesive in which a radiation-curable monomer component or oligomer component is blended with a general pressure-sensitive pressure-sensitive adhesive such as the acrylic pressure-sensitive adhesive or rubber-based pressure-sensitive adhesive. An agent can be illustrated.
- Examples of the radiation curable monomer component to be blended include urethane oligomer, urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol. Stall tetra (meth) acrylate, dipentaerystol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, and the like.
- the radiation curable oligomer component examples 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 compounding amount of the radiation-curable monomer component or oligomer component can be appropriately determined in accordance with the type of the pressure-sensitive adhesive layer, and the amount capable of reducing the 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 a base polymer such as an acrylic polymer constituting the pressure-sensitive adhesive.
- the radiation-curable pressure-sensitive adhesive has a carbon-carbon double bond in the polymer side chain, main chain, or main chain terminal as a base polymer.
- Intrinsic radiation curable pressure sensitive adhesives using Intrinsic radiation curable adhesives do not need to contain oligomer components, which are low molecular components, or do not contain many, so the oligomer components do not move through the adhesive over time and are stable. 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 a radiation-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.
- 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.
- acrylic polymer those obtained by copolymerizing the above-mentioned exemplified hydroxy group-containing monomers, ether compounds of 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, or the like are used.
- the base polymer (particularly acrylic polymer) having the carbon-carbon double bond can be used alone, but the radiation curable monomer does not deteriorate the characteristics.
- Components and oligomer components can also be blended.
- the radiation-curable oligomer component is usually in the range of 30 parts by weight, preferably in the range of 0 to 10 parts by weight, based on 100 parts by weight of the base polymer.
- the radiation 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
- the radiation curable pressure-sensitive adhesive examples include photopolymerizable compounds such as an addition polymerizable compound having two or more unsaturated bonds and an alkoxysilane having an epoxy group disclosed in JP-A-60-196956. And rubber-based pressure-sensitive adhesives and acrylic pressure-sensitive adhesives containing photopolymerization initiators such as carbonyl compounds, organic sulfur compounds, peroxides, amines, and onium salt-based compounds.
- a compound that is colored by irradiation with radiation may be contained as necessary.
- a compound to be colored in the pressure-sensitive adhesive layer 12 by irradiation with radiation By including a compound to be colored in the pressure-sensitive adhesive layer 12 by irradiation with radiation, only the irradiated portion can be colored.
- the compound that is colored by irradiation with radiation is a colorless or light color compound before irradiation with radiation, but becomes a color by irradiation with radiation, and examples thereof include leuco dyes.
- the use ratio of the compound colored by radiation irradiation can be set as appropriate.
- the dicing die-bonding film 10 includes a dicing sheet 1 and an adhesive layer 3 disposed on the pressure-sensitive adhesive layer 12.
- the pressure-sensitive adhesive layer 12 includes a central portion 12a in contact with the adhesive layer 3 and a peripheral portion 12b arranged around the central portion 12a.
- the central portion 12a is a portion cured by radiation irradiation.
- the adhesive layer 3 has thermosetting properties.
- the glass transition temperature of the adhesive layer 3 is preferably 0 ° C. or higher, more preferably 10 ° C. or higher. When the temperature is 0 ° C. or higher, the adhesive layer 3 can be easily divided in a low temperature (for example, 0 ° C. or lower) environment.
- the upper limit of the glass transition temperature of the adhesive layer 3 is, for example, 100 ° C.
- the glass transition temperature of the adhesive layer 3 can be controlled by the glass transition temperature of the acrylic resin.
- the adhesive layer 3 preferably contains a thermoplastic resin.
- Thermoplastic resins 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, thermoplasticity. Examples thereof include 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. Of these thermoplastic resins, an acrylic resin that has few ionic impurities and high heat resistance and can ensure the reliability of the semiconductor element is particularly preferable.
- the acrylic resin is not particularly limited, and one or more 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, is used as a component. And a polymer (acrylic copolymer).
- alkyl group examples include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, cyclohexyl group, 2- Examples include ethylhexyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, lauryl group, tridecyl group, tetradecyl group, stearyl group, octadecyl group, and dodecyl group.
- the other monomer forming the polymer is not particularly limited, and for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid Or a carboxyl group-containing monomer such as crotonic acid, an acid anhydride monomer such as maleic anhydride or itaconic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth ) 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate or (4 -Hydroxymethyl cycle Hexyl) -hydroxyl group-containing monomers such as methyl acrylate, styrene sulfonic
- acrylic resins those having a weight average molecular weight of 100,000 or more are preferable, those having 300,000 to 3,000,000 are more preferable, and those having 500,000 to 2,000,000 are more preferable. It is because it is excellent in adhesiveness and heat resistance in the said numerical range.
- the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
- the adhesive layer 3 preferably contains a thermosetting resin. Thereby, thermal stability can be improved.
- thermosetting resin examples include phenol resin, amino resin, unsaturated polyester resin, epoxy resin, polyurethane resin, silicone resin, and thermosetting polyimide resin.
- an epoxy resin containing a small amount of ionic impurities that corrode semiconductor elements is preferable.
- curing agent of an epoxy resin a phenol resin is preferable.
- the epoxy resin is not particularly limited.
- 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 novolac type.
- Bifunctional epoxy resins such as ortho-cresol novolak type, trishydroxyphenylmethane type, tetraphenylolethane type, etc., and epoxy resins such as hydantoin type, trisglycidyl isocyanurate type, or glycidylamine type are used.
- 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.
- the phenol resin acts as a curing agent for the epoxy resin.
- a novolac type phenol resin such as a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a tert-butylphenol novolak resin, a nonylphenol novolak resin, or a resol type phenol resin.
- polyoxystyrene such as polyparaoxystyrene.
- phenol novolac resins and phenol aralkyl resins are particularly preferred. This is because the connection reliability of the semiconductor device can be improved.
- the mixing 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 product are likely to deteriorate.
- the total content of the epoxy resin and the phenol resin is preferably 100 parts by weight to 1300 parts by weight with respect to 100 parts by weight of the acrylic resin.
- the adhesive layer 3 is previously crosslinked to some extent, it is preferable to add a polyfunctional compound that reacts with a functional group at the molecular chain end of the polymer as a crosslinking agent.
- a polyfunctional compound that reacts with a functional group at the molecular chain end of the polymer as a crosslinking agent.
- adopted as a crosslinking agent 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 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 in the adhesive layer 3 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.
- examples of inorganic fillers 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, lead, Examples thereof include various inorganic powders made of metals such as tin, zinc, palladium, solder, or alloys, and other carbon.
- the adhesive layer 3 preferably contains a thermosetting catalyst.
- the content of the thermosetting catalyst is preferably 0.01 to 3 parts by weight and more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the acrylic resin.
- thermosetting catalyst is not particularly limited, and examples thereof include imidazole compounds, triphenylphosphine compounds, amine compounds, triphenylborane compounds, and trihalogenborane compounds.
- imidazole compounds examples include 2-methylimidazole (trade name; 2MZ), 2-undecylimidazole (trade name; C11Z), 2-heptadecylimidazole (trade name; C17Z), and 1,2-dimethylimidazole (trade name).
- the triphenylphosphine compound is not particularly limited, and examples thereof include triorganophosphine such as triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, and diphenyltolylphosphine.
- triorganophosphine such as triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, and diphenyltolylphosphine.
- Tetraphenylphosphonium bromide (trade name; TPP-PB), methyltriphenylphosphonium (trade name; TPP-MB), methyltriphenylphosphonium chloride (trade name; TPP-MC), methoxymethyltriphenylphosphonium (trade name; TPP-MOC), benzyltriphenylphosphonium chloride (trade name: TPP-ZC), etc. (all manufactured by Hokuko Chemical Co., Ltd.).
- the triphenylborane compound is not particularly limited, and examples thereof include tri (p-methylphenyl) phosphine.
- the triphenylborane compound further includes those having a triphenylphosphine structure.
- the compound having the triphenylphosphine structure and the triphenylborane structure is not particularly limited.
- tetraphenylphosphonium tetraphenylborate (trade name; TPP-K), tetraphenylphosphonium tetra-p-triborate (trade name; TPP-MK), benzyltriphenylphosphonium tetraphenylborate (trade name; TPP-ZK), triphenylphosphine triphenylborane (trade name; TPP-S), and the like (all manufactured by Hokuko Chemical Co., Ltd.).
- the amino compound is not particularly limited, and examples thereof include monoethanolamine trifluoroborate (manufactured by Stella Chemifa Corporation), dicyandiamide (manufactured by Nacalai Tesque Corporation), and the like.
- the trihalogen borane-based compound is not particularly limited, and examples thereof include trichloroborane.
- additives can be appropriately blended in the adhesive layer 3 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.
- silane coupling agent include ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and the like.
- the ion trapping agent include hydrotalcites and bismuth hydroxide.
- the adhesive layer 3 can be manufactured by a usual method. For example, an adhesive composition solution containing each of the above components is prepared, and the adhesive composition solution is applied on a base separator so as to have a predetermined thickness to form a coating film, and then the coating film is dried. Thus, the adhesive layer 3 can be manufactured.
- the solvent used in the adhesive composition solution is not particularly limited, but an organic solvent capable of uniformly dissolving, kneading or dispersing the above components is preferable.
- organic solvent capable of uniformly dissolving, kneading or dispersing the above components is preferable.
- examples thereof include ketone solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone, and cyclohexanone, toluene, xylene, and the like.
- the application method is not particularly limited. Examples of the solvent coating method include a die coater, a gravure coater, a roll coater, a reverse coater, a comma coater, a pipe doctor coater, and screen printing. Of these, a die coater is preferable in terms of high uniformity of coating thickness.
- polyethylene terephthalate (PET), polyethylene, 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 can be used.
- a release agent such as a fluorine-type release agent or a long-chain alkyl acrylate release agent
- Examples of the method for applying the adhesive composition solution include roll coating, screen coating, and gravure coating.
- the drying conditions for the coating film are not particularly limited, and for example, the drying can be performed at a drying temperature of 70 to 160 ° C. and a drying time of 1 to 5 minutes.
- a method for producing the adhesive layer 3 for example, a method of producing the adhesive layer 3 by mixing the respective components with a mixer and press-molding the obtained mixture is also suitable.
- a planetary mixer etc. are mentioned as a mixer.
- the thickness of the adhesive layer 3 is not particularly limited, but is preferably 5 ⁇ m or more, and more preferably 15 ⁇ m or more.
- the thickness of the adhesive layer 3 is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
- the adhesive layer 3 can be used as a die attach film for bonding an adherend such as a lead frame and a semiconductor element.
- adherend such as a lead frame and a semiconductor element.
- the adherend include a lead frame, an interposer, and a semiconductor element.
- the adhesive layer 3 is preferably protected by a separator (not shown).
- the separator has a function as a protective material that protects the adhesive layer 3 until it is put to practical use.
- the separator is peeled off when the semiconductor wafer is attached to the adhesive layer 3.
- PET polyethylene terephthalate
- polyethylene polyethylene
- polypropylene polypropylene
- a plastic film or paper whose surface is coated with a release agent such as a fluorine release agent or a long-chain alkyl acrylate release agent.
- the dicing die bond film 10 can be manufactured by a normal method.
- the dicing die-bonding film 10 can be manufactured by bonding the dicing sheet 1 and the adhesive layer 3 together.
- the dicing die bond film 10 can be used for manufacturing a semiconductor device.
- the condensing point is aligned inside the semiconductor wafer 4P, and the laser beam 100 is irradiated along the lattice-shaped division planned line 4L, thereby forming the modified region 41 inside the semiconductor wafer 4P. Thereby, the divided wafer 4 is obtained.
- the irradiation conditions of the laser beam 100 can be adjusted as appropriate within the range of the following conditions, for example.
- B Condensing lens Magnification 100 times or less NA 0.55 Transmittance with respect to laser light wavelength: 100% or less
- the divided wafer 4 includes a modified region 41.
- the divided wafer 4 further includes semiconductor elements 5A, 5B, 5C,.
- both sides are defined by the front surface (Otemen) and the back surface facing the front surface.
- the surface is a surface on which a circuit is provided.
- the back surface is a surface on which no circuit is provided.
- the back surface of the divided wafer 4 is ground to make the divided wafer 4 thinner.
- the divided wafer 4 is pressure-bonded to the adhesive layer 3 to obtain a laminate 21.
- the laminate 21 includes the dicing die bond film 10 and the divided wafer 4 disposed on the adhesive layer 3.
- a dicing ring 31 is attached to the peripheral portion 12b.
- the dicing sheet 1 is expanded by raising the push-up portion 33 disposed below the laminated body 21, and the divided wafer 4 and the adhesive layer 3 are divided from the modified region 41 as a starting point.
- positioned on the dicing sheet 1 and the adhesive layer 12 is obtained.
- the die bonding chip 2A includes an adhesive film 22A and a semiconductor element 5A disposed on the adhesive film 22A.
- the die bonding chip 2B includes an adhesive film 22B and a semiconductor element 5B arranged on the adhesive film 22B.
- the die bonding chip 2C includes an adhesive film 22C and a semiconductor element 5C disposed on the adhesive film 22C.
- the die bonding chip 2D includes an adhesive film 22D and a semiconductor element 5D arranged on the adhesive film 22D.
- the die bonding chip 2E includes an adhesive film 22E and a semiconductor element 5E disposed on the adhesive film 22E.
- the die-bonding chip 2F includes an adhesive film 22F and a semiconductor element 5F disposed on the adhesive film 22F.
- the die-bonding chip 2G includes an adhesive film 22G and a semiconductor element 5G disposed on the adhesive film 22G.
- the die bonding chip 2H includes an adhesive film 22H and a semiconductor element 5H disposed on the adhesive film 22H.
- the adhesive films 22A, 22B, 22C,..., 22H are in contact with the pressure-sensitive adhesive layer 12.
- the dicing sheet 1 is expanded at 10 ° C. or lower. More preferably, the expansion is performed at 0 ° C. or less.
- the adhesive bond layer 3 can be parted easily as it is 0 degrees C or less.
- the lower limit of the temperature is not particularly limited, and is ⁇ 20 ° C., for example.
- the speed at which the push-up portion 33 rises is preferably 0.1 mm / second or more, more preferably 1 mm / second or more. If it is 0.1 mm / second or more, it can be easily divided. On the other hand, the upper limit of the expanding speed is not particularly limited.
- the push-up portion 33 is lowered.
- sagging occurs in the peripheral portion 12b.
- the dicing sheet 1 is expanded by raising the suction table 32 arranged below the divided structure 51, and the dicing sheet 1 is sucked by the suction table 32 while maintaining the expansion.
- the suction table 32 is lowered while the dicing sheet 1 is sucked by the suction table 32.
- the temperature of the hot air is preferably 220 ° C. or higher, more preferably 250 ° C. or higher.
- the peripheral part 12b can be easily contracted as it is 220 degreeC or more.
- the hot air is heated at a temperature of preferably 400 ° C. or lower, more preferably 300 ° C. or lower. When the temperature is 400 ° C. or lower, the dicing sheet 1 can be prevented from being damaged.
- the pressure-sensitive adhesive layer 12 is an ultraviolet curable type
- the pressure-sensitive adhesive layer 12 is cured by irradiating the pressure-sensitive adhesive layer 12 with ultraviolet rays.
- tip 2 for die-bonding of the adhesive layer 12 can be reduced.
- Conditions such as irradiation intensity and irradiation time at the time of ultraviolet irradiation are not particularly limited, and may be set as necessary.
- the pressure-sensitive adhesive layer 12 is not an ultraviolet curable type, it is not necessary to irradiate the pressure-sensitive adhesive layer 12 with ultraviolet rays.
- the pickup method is not particularly limited, and various conventionally known methods can be employed. For example, there is a method of pushing up the die bonding chip 2A with a needle and picking up the pushed up die bonding chip 2A with a pickup device.
- the die bonding chip 2A is pressure-bonded to the adherend 6 to obtain an adherend 61 with a semiconductor element.
- the adherend 61 with a semiconductor element includes an adherend 6, an adhesive film 22 ⁇ / b> A disposed on the adherend 6, and a semiconductor element 5 ⁇ / b> A disposed on the adhesive film 22 ⁇ / b> A.
- the crimping temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher.
- the pressure bonding temperature is preferably 150 ° C. or lower, more preferably 130 ° C. or lower.
- the adhesive film 22A is thermally cured, and the semiconductor element 5A is fixed to the adherend 6.
- thermally cure the adhesive film 22A by heating the adherend 61 with a semiconductor element under pressure.
- thermally curing the adhesive film 22A under pressure By thermally curing the adhesive film 22A under pressure, voids existing between the adhesive film 22A and the adherend 6 can be easily eliminated.
- Examples of the method of heating under pressure include a method of heating the adherend 61 with a semiconductor element arranged in a chamber filled with an inert gas.
- the pressure of the pressurized atmosphere is preferably 0.5 kg / cm 2 (4.9 ⁇ 10 ⁇ 2 MPa) or more, more preferably 1 kg / cm 2 (9.8 ⁇ 10 ⁇ 2 MPa) or more, and further preferably 5 kg. / Cm 2 (4.9 ⁇ 10 ⁇ 1 MPa) or more. If it is 0.5 kg / cm 2 or more, voids existing between the adhesive film 22A and the adherend 6 can be easily eliminated.
- the pressure of the pressurized atmosphere is preferably 20kg / cm 2 (1.96MPa), more preferably 18kg / cm 2 (1.77MPa) or less, more preferably not more than 15kg / cm 2 (1.47MPa).
- the protrusion of the adhesive film 22A due to excessive pressurization can be suppressed as it is 20 kg / cm 2 or less.
- the heating temperature at the time of heating under pressure is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, further preferably 120 ° C. or higher, and particularly preferably 170 ° C. or higher.
- the adhesive film 22A can have an appropriate hardness, and voids can be effectively eliminated by pressure curing.
- the heating temperature is preferably 260 ° C. or lower, more preferably 200 ° C. or lower, more preferably 180 ° C. or lower. When the temperature is 260 ° C. or lower, the adhesive film 22A can be prevented from being decomposed.
- the heating time is preferably 0.1 hour or longer, more preferably 0.2 hour or longer, and further preferably 0.5 hour or longer. When it is 0.1 hour or longer, the effect of pressurization can be sufficiently obtained.
- the heating time is preferably 24 hours or less, more preferably 3 hours or less, and even more preferably 1 hour or less.
- a wire bonding step of electrically connecting the tip of the terminal portion (inner lead) of the adherend 6 and an electrode pad (not shown) on the semiconductor element 5A with a bonding wire 7 is performed.
- the bonding wire 7 for example, a gold wire, an aluminum wire or a copper wire is used.
- the temperature during wire bonding is preferably 80 ° C. or higher, more preferably 120 ° C. or higher, and the temperature is preferably 250 ° C. or lower, more preferably 175 ° C. or lower.
- the heating time is several seconds to several minutes (for example, 1 second to 1 minute).
- the connection is performed by a combination of vibration energy by ultrasonic waves and pressure energy by pressurization while being heated so as to be within the temperature range.
- a sealing step of sealing the semiconductor element 5A with the sealing resin 8 is performed.
- This step is performed to protect the semiconductor element 5 ⁇ / b> A and the bonding wire 7 mounted on the adherend 6.
- This step is performed by molding a sealing resin with a mold.
- the sealing resin 8 for example, an epoxy resin is used.
- the heating temperature at the time of resin sealing is preferably 165 ° C. or higher, more preferably 170 ° C. or higher, and the heating temperature is preferably 185 ° C. or lower, more preferably 180 ° C. or lower.
- the sealing resin 8 which is insufficiently cured in the sealing process can be completely cured.
- the heating temperature can be set as appropriate.
- Modification 1 In the first modification, the semiconductor wafer 4P is pressure-bonded to the dicing die-bonding film 10. Next, the modified region 41 is formed inside the semiconductor wafer 4 ⁇ / b> P disposed on the dicing die bond film 10 to obtain the divided wafer 4.
- Modification 2 In Modification 2, the wire bonding step is performed without thermosetting the adhesive film 22A.
- the peripheral part 12b is a part cured by radiation irradiation.
- the central portion 12a is a portion that is not cured by radiation irradiation.
- the manufacturing method of the semiconductor device according to the first embodiment is a process of preparing the divided body 21 including the dicing die bond film 10 and the divided wafer 4 including the modified region 41 disposed on the adhesive layer 3. Then, by expanding the dicing sheet 1, after the step of dividing the divided wafer 4 and the adhesive layer 3 from the modified region 41 and the step of dividing the divided wafer 4 and the adhesive layer 3, the peripheral portion 12 b Heating.
- the manufacturing method of the semiconductor device of Embodiment 1 further includes a step of pressure bonding the die bonding chip 2A obtained by the step of dividing the divided wafer 4 and the adhesive layer 3 to the adherend 6 and the like.
- the step of preparing the divided body 21 includes a step of forming the divided wafer 4.
- the step of forming the divided wafer 4 includes a step of forming the modified region 41 inside the semiconductor wafer 4P by irradiating the laser beam 100 along the planned division line 4L.
- Base material Fanclaire NRB # 115 (ethylene vinyl acetate copolymer film) manufactured by Gunze Base material B: Fanclaire NRB # 135 (ethylene vinyl acetate copolymer film) manufactured by Gunze Base material C: PE-5 (ethylene-acrylic acid ester copolymer film) manufactured by Aussie Film Base material D: HL film (polyvinyl chloride film) manufactured by Ron Seal Industry Co., Ltd.
- Substrate E PP-1 (polypropylene film) manufactured by Aussie Film Base material
- F Polypropylene (80%) polyethylene (20%) two-layer film
- Base material G Polypropylene (80%) polyethylene (20%) two-layer film
- Example 1 [Production of dicing die bond film] (Example 1) In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, 86.4 parts of 2-ethylhexyl acrylate (hereinafter also referred to as “2EHA”), 2-hydroxyethyl acrylate ( Hereinafter, it is also referred to as “HEA”.) 13.6 parts, 0.2 part of benzoyl peroxide, and 65 parts of toluene are put into a nitrogen gas stream and polymerized at 61 ° C. for 6 hours to obtain acrylic polymer B. Obtained.
- 2EHA 2-ethylhexyl acrylate
- HOA 2-hydroxyethyl acrylate
- acrylic polymer B 14.6 parts of 2-methacryloyloxyethyl isocyanate (hereinafter also referred to as “MOI”) was added, and an addition reaction treatment was carried out in an air stream at 50 ° C. for 48 hours to obtain acrylic polymer B ′.
- MOI 2-methacryloyloxyethyl isocyanate
- the pressure-sensitive adhesive composition solution was applied on a release treatment film and dried by heating at 120 ° C.
- the obtained dicing sheet has the adhesive layer arrange
- Acrylic resin, epoxy resin A, epoxy resin B, phenol resin, silica, and catalyst were dissolved in methyl ethyl ketone at a ratio shown in Table 2 to prepare an adhesive composition solution having a concentration of 40 to 50% by weight.
- Acrylic resin SG-708-6 (Tg: 4 ° C) manufactured by Nagase ChemteX Corporation
- Epoxy resin A KI-3000 (solid) manufactured by Toto Kasei Co., Ltd.
- Epoxy resin B JER YL980 (liquid) manufactured by Mitsubishi Chemical Corporation
- Phenolic resin MEH-7800H (solid) manufactured by Meiwa Kasei Co., Ltd.
- Silica SE-2050MC manufactured by Admatechs Co., Ltd. (average particle size: 0.5 ⁇ m)
- Catalyst TPP-K manufactured by Hokuko Chemical Co., Ltd.
- the prepared adhesive composition solution was applied to a 50 ⁇ m-thick polyethylene terephthalate film subjected to silicone release treatment, and then dried at 130 ° C. for 2 minutes to prepare an adhesive coating film having a thickness of 30 ⁇ m. A circular adhesive layer having a diameter of 330 mm was cut out from the adhesive coating film.
- a circular adhesive layer was bonded to the pressure-sensitive adhesive layer to prepare a dicing die-bonding film.
- Example 2 A dicing die-bonding film was produced in the same manner as in Example 1 except that the base material B was used instead of the base material A.
- Example 3 A dicing die-bonding film was produced in the same manner as in Example 1 except that the substrate C was used instead of the substrate A.
- Example 4 A dicing die-bonding film was produced in the same manner as in Example 1 except that the substrate D was used instead of the substrate A.
- Example 1 A dicing die-bonding film was produced in the same manner as in Example 1 except that the substrate E was used instead of the substrate A.
- Comparative Example 2 A dicing die-bonding film was produced in the same manner as in Example 1 except that the base material F was used instead of the base material A.
- a dicing sheet was obtained by removing the adhesive layer from the dicing die-bonding film.
- a tensile tester Autograph, manufactured by Shimadzu Corporation
- a tensile test was performed under the conditions of 23 ° C., a tensile speed of 300 mm / min, and a distance between chucks of 100 mm. I read it.
- a dicing sheet was obtained by removing the adhesive layer from the dicing die-bonding film.
- a tensile tester Autograph, manufactured by Shimadzu Corporation
- a tensile test was performed under the conditions of 23 ° C., a tensile speed of 300 mm / min, and a distance between chucks of 100 mm. I read it.
- the focusing point is aligned with the interior of a 12 inch semiconductor wafer, and the surface of the semiconductor wafer (10 mm ⁇ 10 mm) along the planned dividing line (10 mm ⁇ 10 mm) Otemen) or laser light was irradiated from the back side to form a modified region inside the semiconductor wafer. Thereafter, a protective tape for back grinding was bonded to the surface of the semiconductor wafer, and the back surface was ground using a disco back grinder DGP8760 so that the thickness of the semiconductor wafer was 30 ⁇ m.
- the laser light irradiation conditions are shown below.
- a sample was obtained by cleaving the semiconductor wafer and heat shrinking the dicing sheet. That is, first, the semiconductor wafer was cleaved by a cool expander unit under the conditions of an expansion temperature of ⁇ 15 ° C., an expansion speed of 200 mm / second, and an expansion amount of 12 mm. Then, the sample was obtained by heat-shrinking the dicing sheet with a heat expander unit under the conditions of an expansion amount of 10 mm, a heat temperature of 250 ° C., an air volume of 40 L / min, a heat distance of 20 mm, and a rotation speed of 3 ° / sec. The sample was evaluated for pickup using a die bonder SPA-300 manufactured by Shinkawa Co., Ltd.
- the adhesive layer was laminated to a thickness of 300 ⁇ m under the condition of 60 ° C., and then a strip-shaped measurement piece having a length of 30 mm and a width of 10 mm was cut out.
- RSA dynamic viscoelasticity measuring device
- the storage elastic modulus and the loss elastic modulus at ⁇ 30 ° C. to 100 ° C. were measured as the distance between chucks of 22.5 mm, Measurement was performed under conditions of a frequency of 1 Hz and a heating rate of 10 ° C./min, and a glass transition temperature was obtained from the peak value of tan ⁇ .
- Dicing die bond film 1 Dicing sheet 2A, 2B, 2C, 2D, 2E, 2F, 2G, 2H Die bonding chip 3 Adhesive layer 4P Semiconductor wafer 4L Divided line 4 Divided wafers 5A, 5B, 5C, 5D, 5E, 5F, 5G, 5H Semiconductor element 6 Substrate 7 Bonding wire 8 Sealing resin 11 Base material 12 Adhesive layer 12a Central part 12b Peripheral part 21 Laminated bodies 22A, 22B, 22C, 22D, 22E, 22F, 22G, 22H Adhesion Film 31 Dicing ring 32 Suction table 33 Push-up portion 41 Modified region 51 Divided structure 61 Substrate with semiconductor element 100 Laser beam
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Abstract
Provided is a dicing sheet and a dicing/die-bonding film with which it is possible to eliminate sagging of the dicing sheet and to prevent contact between semiconductor elements. The present invention relates to a dicing sheet that contracts as a result of being heated for 1 minute at 100°C, with a second length in the MD direction after heating being 95% or less of 100% of a first length in the MD direction before heating. The dicing sheet is provided with a substrate, and a pressure-sensitive adhesive layer disposed on the substrate. The dicing/die-bonding film is provided with the dicing sheet, and an adhesive layer disposed on the pressure-sensitive adhesive layer.
Description
本発明は、ダイシングシート、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に関する。
The present invention relates to a dicing sheet, a dicing die-bonding film, and a method for manufacturing a semiconductor device.
図１３、図１４に示すように、基材９１１及び基材９１１上に配置された粘着剤層９１２を有するダイシングシート９０１並びに粘着剤層９１２上に配置された接着剤層９０３を有するダイシング・ダイボンドフィルム９１０を用いる半導体装置の製造技術に関して、半導体素子９０５Ａ、９０５Ｂ、９０５Ｃ、……、９０５Ｈ及び改質領域９４１を有するウエハ９０４を接着剤層９０３に圧着し、ダイシングシート９０１を拡張することにより、改質領域９４１を起点にウエハ９０４及び接着剤層９０３を分断する方法などが知られている（例えば、特許文献１、２参照）。
As shown in FIGS. 13 and 14, a dicing die bond having a base material 911 and a dicing sheet 901 having an adhesive layer 912 disposed on the base material 911 and an adhesive layer 903 disposed on the adhesive layer 912. Regarding the manufacturing technology of the semiconductor device using the film 910, by bonding the wafer 904 having the semiconductor elements 905A, 905B, 905C,..., 905H and the modified region 941 to the adhesive layer 903 and expanding the dicing sheet 901, A method of dividing the wafer 904 and the adhesive layer 903 starting from the modified region 941 is known (see, for example, Patent Documents 1 and 2).
図１５に示すように、拡張を解いた後、周辺部９１２ｂがたるむ。周辺部９１２ｂのたるみを放置すると、半導体素子９０５Ａと半導体素子９０５Ｂ、半導体素子９０５Ｂと半導体素子９０５Ｃ、……半導体素子９０５Ｇと半導体素子９０５Ｈが接触することがある。
As shown in FIG. 15, the peripheral portion 912b sags after the expansion is solved. If the slack in the peripheral portion 912b is left unattended, the semiconductor elements 905A and 905B, the semiconductor elements 905B and 905C,..., May contact the semiconductor elements 905G and 905H.
本発明は前記課題を解決し、たるみを取り除くことが可能で、半導体素子同士の接触を防止できるダイシングシートを提供することを目的とする。
An object of the present invention is to provide a dicing sheet that can solve the above-described problems and remove sagging and prevent contact between semiconductor elements.
本発明は、１００℃で１分加熱することにより収縮し、加熱前のＭＤ方向の第１長さ１００％に対して加熱後のＭＤ方向の第２長さは９５％以下であるダイシングシートに関する。第１長さ１００％に対して第２長さは９５％以下であるので、加熱によりたるみを取り除くことが可能で、半導体素子同士の接触を防止できる。
The present invention relates to a dicing sheet that shrinks when heated at 100 ° C. for 1 minute, and whose second length in the MD direction after heating is 95% or less with respect to the first length in the MD direction before heating of 100%. . Since the second length is 95% or less with respect to the first length of 100%, sagging can be removed by heating, and contact between the semiconductor elements can be prevented.
本発明のダイシングシートは、好ましくは次の性質を備える。すなわち、２３℃でＭＤ方向に３％伸ばしたときの引張応力は１Ｎ／ｍｍ２以上である。１Ｎ／ｍｍ２以上であると、半導体ウェハ割断時に適度な引張応力がかかるので、半導体ウェハを割断可能で半導体素子同士の間隔をあけることができる。
The dicing sheet of the present invention preferably has the following properties. That is, the tensile stress when stretched by 3% in the MD direction at 23 ° C. is 1 N / mm 2 or more. When it is 1 N / mm 2 or more, an appropriate tensile stress is applied at the time of cleaving the semiconductor wafer, so that the semiconductor wafer can be cleaved and the semiconductor elements can be spaced apart.
本発明のダイシングシートは、好ましくは次の性質を備える。すなわち、２３℃でＭＤ方向に６％伸ばしたときの引張応力は１．５Ｎ／ｍｍ２以上である。１．５Ｎ／ｍｍ２以上であると、半導体ウェハ割断時に適度な引張応力がかかるので、半導体ウェハを割断可能で半導体素子同士の間隔をあけることができる。
The dicing sheet of the present invention preferably has the following properties. That is, the tensile stress when stretched 6% in the MD direction at 23 ° C. is 1.5 N / mm 2 or more. When it is 1.5 N / mm 2 or more, an appropriate tensile stress is applied at the time of cleaving the semiconductor wafer, so that the semiconductor wafer can be cleaved and the semiconductor elements can be spaced apart.
本発明のダイシングシートの厚みは、好ましくは４０μｍ～２００μｍである。本発明のダイシングシートは、通常、基材及び基材上に配置された粘着剤層を備える。
The thickness of the dicing sheet of the present invention is preferably 40 μm to 200 μm. The dicing sheet of the present invention usually comprises a base material and an adhesive layer disposed on the base material.
本発明はまた、ダイシングシートと、粘着剤層上に配置された接着剤層とを備えるダイシング・ダイボンドフィルムに関する。接着剤層のガラス転移温度は、好ましくは０℃以上である。好ましくは、粘着剤層が、接着剤層と接した中央部及び中央部の周辺に配置された周辺部を備える。
The present invention also relates to a dicing die-bonding film comprising a dicing sheet and an adhesive layer disposed on the pressure-sensitive adhesive layer. The glass transition temperature of the adhesive layer is preferably 0 ° C. or higher. Preferably, the pressure-sensitive adhesive layer includes a central portion in contact with the adhesive layer and a peripheral portion disposed around the central portion.
本発明はまた、分割体を準備する工程と、ダイシングシートを拡張することにより、改質領域を起点に分割ウエハ及び接着剤層を分断する工程と、分割ウエハ及び接着剤層を分断する工程の後に、周辺部を加熱する工程とを含む半導体装置の製造方法に関する。分割体は、ダイシング・ダイボンドフィルム、及び接着剤層上に配置された分割ウエハを備える。分割ウエハが改質領域を備える。
The present invention also includes a step of preparing the divided body, a step of dividing the divided wafer and the adhesive layer from the modified region by expanding the dicing sheet, and a step of dividing the divided wafer and the adhesive layer. And a step of heating a peripheral portion later. The divided body includes a dicing die-bonding film and a divided wafer disposed on the adhesive layer. The divided wafer has a modified region.
以下に実施形態を掲げ、本発明を詳細に説明するが、本発明はこれらの実施形態のみに限定されるものではない。
Hereinafter, the present invention will be described in detail with reference to embodiments, but the present invention is not limited only to these embodiments.
［実施形態１］
（ダイシングシート１）
図１に示すように、ダイシングシート１は、基材１１及び基材１１上に配置された粘着剤層１２を備える。 [Embodiment 1]
(Dicing sheet 1)
As shown in FIG. 1, thedicing sheet 1 includes a base material 11 and an adhesive layer 12 arranged on the base material 11.
（ダイシングシート１）
図１に示すように、ダイシングシート１は、基材１１及び基材１１上に配置された粘着剤層１２を備える。 [Embodiment 1]
(Dicing sheet 1)
As shown in FIG. 1, the
ダイシングシート１は次の性質を備える。すなわち、１００℃で１分加熱することにより収縮し、加熱前のＭＤ（Ｍａｃｈｉｎｅ Ｄｉｒｅｃｔｉｏｎ）方向の第１長さ１００％に対して加熱後のＭＤ方向の第２長さは９５％以下である。第１長さ１００％に対して第２長さは、好ましくは９６％以下である。一方、第１長さ１００％に対して第２長さは、例えば、５０％以上である。
Dicing sheet 1 has the following properties. That is, it shrinks by heating at 100 ° C. for 1 minute, and the second length in the MD direction after heating is 95% or less with respect to the first length 100% in the MD (Machine Direction) direction before heating. The second length is preferably 96% or less with respect to the first length of 100%. On the other hand, the second length is, for example, 50% or more with respect to the first length of 100%.
第２長さの第１長さに対する比の値は、基材１１の材料、基材１１の製膜方法によりコントロールできる。なかでも、基材１１の製膜方法が、第２長さの第１長さに対する比の値に与える影響が大きい。例えば、基材１１を延伸することにより、第２長さの第１長さに対する比の値を小さくすることができる。
The value of the ratio of the second length to the first length can be controlled by the material of the base material 11 and the film forming method of the base material 11. Especially, the influence which the film forming method of the base material 11 has on the value of the ratio of the second length to the first length is great. For example, by stretching the substrate 11, the value of the ratio of the second length to the first length can be reduced.
ダイシングシート１は、好ましくは次の性質を備える。すなわち、２３℃でＭＤ方向に３％伸ばしたときの引張応力は、好ましくは１Ｎ／ｍｍ２以上である。１Ｎ／ｍｍ２以上であると、半導体ウェハ割断時に適度な引張応力がかかるので、半導体ウェハを割断可能で半導体素子同士の間隔をあけることができる。また、半導体素子同士の間隔を維持できる。２３℃でＭＤ方向に３％伸ばしたときの引張応力の上限は、例えば、１５Ｎ／ｍｍ２である。
The dicing sheet 1 preferably has the following properties. That is, the tensile stress when stretched by 3% in the MD direction at 23 ° C. is preferably 1 N / mm 2 or more. When it is 1 N / mm 2 or more, an appropriate tensile stress is applied at the time of cleaving the semiconductor wafer, so that the semiconductor wafer can be cleaved and the semiconductor elements can be spaced apart. In addition, the distance between the semiconductor elements can be maintained. The upper limit of the tensile stress when extending 3% in the MD direction at 23 ° C. is, for example, 15 N / mm 2 .
ダイシングシート１は、好ましくは次の性質を備える。すなわち、２３℃でＭＤ方向に６％伸ばしたときの引張応力は、好ましくは１．５Ｎ／ｍｍ２以上である。１．５Ｎ／ｍｍ２以上であると、半導体ウェハ割断時に適度な引張応力がかかるので、半導体ウェハを割断可能で半導体素子同士の間隔をあけることができる。また、半導体素子同士の間隔を維持できる。２３℃でＭＤ方向に６％伸ばしたときの引張応力の上限は、例えば、２０Ｎ／ｍｍ２である。
The dicing sheet 1 preferably has the following properties. That is, the tensile stress when stretched 6% in the MD direction at 23 ° C. is preferably 1.5 N / mm 2 or more. When it is 1.5 N / mm 2 or more, an appropriate tensile stress is applied at the time of cleaving the semiconductor wafer, so that the semiconductor wafer can be cleaved and the semiconductor elements can be spaced apart. In addition, the distance between the semiconductor elements can be maintained. The upper limit of the tensile stress when extending 6% in the MD direction at 23 ° C. is, for example, 20 N / mm 2 .
ダイシングシート１の厚みは、好ましくは４０μｍ以上、より好ましくは６０μｍ以上である。一方、ダイシングシート１の厚みは、好ましくは２００μｍ以下、より好ましくは１８０μｍ以下である。
The thickness of the dicing sheet 1 is preferably 40 μm or more, more preferably 60 μm or more. On the other hand, the thickness of the dicing sheet 1 is preferably 200 μm or less, more preferably 180 μm or less.
ダイシングシート１の厚みを１００％としたとき、基材１１の厚みは好ましくは５０％以上、より好ましくは７０％以上である。一方、基材１１の厚みは好ましくは９８％以下、より好ましくは９５％以下である。
When the thickness of the dicing sheet 1 is 100%, the thickness of the substrate 11 is preferably 50% or more, more preferably 70% or more. On the other hand, the thickness of the base material 11 is preferably 98% or less, more preferably 95% or less.
基材１１としては、例えば、ポリエチレンテレフタレートフィルム、ポリエチレンフィルム、ポリスチレンフィルム、ポリプロピレンフィルム、ポリアミドフィルム、ポリウレタンフィルム、ポリ塩化ビニリデンフィルム、ポリ塩化ビニルフィルム、エチレン酢酸ビニル共重合体フィルム、エチレン－アクリル酸エステル共重合体フィルム、ポリ塩化ビニルフィルムなどが挙げられる。
Examples of the substrate 11 include a polyethylene terephthalate film, a polyethylene film, a polystyrene film, a polypropylene film, a polyamide film, a polyurethane film, a polyvinylidene chloride film, a polyvinyl chloride film, an ethylene vinyl acetate copolymer film, and an ethylene-acrylic ester. A copolymer film, a polyvinyl chloride film, etc. are mentioned.
基材１１としては、無延伸フィルム、一軸延伸フィルム、二軸延伸フィルムなどを使用できる。なかでも、異方性がないという理由から、無延伸フィルムが好ましい。
As the substrate 11, an unstretched film, a uniaxially stretched film, a biaxially stretched film, or the like can be used. Among these, an unstretched film is preferable because it has no anisotropy.
基材１１の構造としては、単層、複層などが挙げられる。
The structure of the base material 11 includes a single layer, a multilayer, and the like.
基材１１の表面は、隣接する層との密着性、保持性などを高める為、慣用の表面処理、例えば、クロム酸処理、オゾン暴露、火炎暴露、高圧電撃暴露、イオン化放射線処理などの化学的又は物理的処理、下塗剤（例えば、後述する粘着物質）によるコーティング処理を施すことができる。
The surface of the base material 11 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. Alternatively, a physical treatment or a coating treatment with a primer (for example, an adhesive substance described later) can be performed.
粘着剤層１２の形成に用いる粘着剤としては特に制限されず、例えば、アクリル系粘着剤、ゴム系粘着剤などの一般的な感圧性接着剤を用いることができる。感圧性接着剤としては、半導体ウエハやガラスなどの汚染をきらう電子部品の超純水やアルコールなどの有機溶剤による清浄洗浄性などの点から、アクリル系ポリマーをベースポリマーとするアクリル系粘着剤が好ましい。
The pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer 12 is not particularly limited, and for example, a general pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive can be used. As pressure-sensitive adhesives, acrylic adhesives based on acrylic polymers are used as the base polymer from the standpoint of cleanability of electronic components that are difficult to contaminate such as semiconductor wafers and glass with organic solvents such as ultrapure water and alcohol. preferable.
アクリル系ポリマーとしては、例えば、（メタ）アクリル酸アルキルエステル（例えば、メチルエステル、エチルエステル、プロピルエステル、イソプロピルエステル、ブチルエステル、イソブチルエステル、ｓ－ブチルエステル、ｔ－ブチルエステル、ペンチルエステル、イソペンチルエステル、ヘキシルエステル、ヘプチルエステル、オクチルエステル、２－エチルヘキシルエステル、イソオクチルエステル、ノニルエステル、デシルエステル、イソデシルエステル、ウンデシルエステル、ドデシルエステル、トリデシルエステル、テトラデシルエステル、ヘキサデシルエステル、オクタデシルエステル、エイコシルエステルなどのアルキル基の炭素数１～３０、特に炭素数４～１８の直鎖状又は分岐鎖状のアルキルエステルなど）及び（メタ）アクリル酸シクロアルキルエステル（例えば、シクロペンチルエステル、シクロヘキシルエステルなど）の１種又は２種以上を単量体成分として用いたアクリル系ポリマーなどが挙げられる。なお、（メタ）アクリル酸エステルとはアクリル酸エステル及び／又はメタクリル酸エステルをいい、本発明の（メタ）とは全て同様の意味である。
Examples of the acrylic polymer 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, Pentyl 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, Straight chain or branched chain alkyl esters having 1 to 30 carbon atoms, particularly 4 to 18 carbon atoms, such as octadecyl ester and eicosyl ester) and (Meth) acrylic acid cycloalkyl esters (e.g., cyclopentyl ester, cyclohexyl ester, etc.), etc. One or acrylic polymer using two or more of the monomer component thereof. In addition, (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester, and (meth) of the present invention has the same meaning.
アクリル系ポリマーは、凝集力、耐熱性などの改質を目的として、必要に応じ、前記（メタ）アクリル酸アルキルエステル又はシクロアルキルエステルと共重合可能な他のモノマー成分に対応する単位を含んでいてもよい。この様なモノマー成分として、例えば、アクリル酸、メタクリル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸などのカルボキシル基含有モノマー；無水マレイン酸、無水イタコン酸などの酸無水物モノマー；（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸６－ヒドロキシヘキシル、（メタ）アクリル酸８－ヒドロキシオクチル、（メタ）アクリル酸１０－ヒドロキシデシル、（メタ）アクリル酸１２－ヒドロキシラウリル、（４－ヒドロキシメチルシクロヘキシル）メチル（メタ）アクリレートなどのヒドロキシル基含有モノマー；スチレンスルホン酸、アリルスルホン酸、２－（メタ）アクリルアミド－２－メチルプロパンスルホン酸、（メタ）アクリルアミドプロパンスルホン酸、スルホプロピル（メタ）アクリレート、（メタ）アクリロイルオキシナフタレンスルホン酸などのスルホン酸基含有モノマー；２－ヒドロキシエチルアクリロイルホスフェートなどのリン酸基含有モノマー；アクリルアミド、アクリロニトリルなどが挙げられる。これら共重合可能なモノマー成分は、１種又は２種以上使用できる。これら共重合可能なモノマーの使用量は、全モノマー成分の４０重量％以下が好ましい。
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. May be. Examples of 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; Sti Contains sulfonic acid groups such as ethylene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid Monomers; Phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate; acrylamide, acrylonitrile and the like. One or more of these copolymerizable monomer components can be used. The amount of these copolymerizable monomers used is preferably 40% by weight or less based on the total monomer components.
更に、アクリル系ポリマーは、架橋させる為、多官能性モノマーなども、必要に応じて共重合用モノマー成分として含むことができる。この様な多官能性モノマーとして、例えば、ヘキサンジオールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート、ウレタン（メタ）アクリレートなどが挙げられる。これらの多官能性モノマーも１種又は２種以上用いることができる。多官能性モノマーの使用量は、粘着特性などの点から、全モノマー成分の３０重量％以下が好ましい。
Furthermore, since the acrylic polymer is cross-linked, 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 30% by weight or less of the total monomer components from the viewpoint of adhesive properties and the like.
アクリル系ポリマーは、単一モノマー又は２種以上のモノマー混合物を重合に付すことにより得られる。重合は、溶液重合、乳化重合、塊状重合、懸濁重合などの何れの方式で行うこともできる。清浄な被着体への汚染防止などの点から、低分子量物質の含有量が小さいのが好ましい。この点から、アクリル系ポリマーの数平均分子量は、好ましくは３０万以上、更に好ましくは４０万～３００万程度である。
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 carried out by any method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like. From the viewpoint of preventing contamination of a clean adherend, it is preferable that the content of the low molecular weight substance is small. From this point, the number average molecular weight of the acrylic polymer is preferably 300,000 or more, more preferably about 400,000 to 3 million.
また、前記粘着剤には、ベースポリマーであるアクリル系ポリマーなどの数平均分子量を高める為、外部架橋剤を適宜に採用することもできる。外部架橋方法の具体的手段としては、ポリイソシアネート化合物、エポキシ化合物、アジリジン化合物、メラミン系架橋剤などのいわゆる架橋剤を添加し反応させる方法が挙げられる。外部架橋剤を使用する場合、その使用量は、架橋すべきベースポリマーとのバランスにより、更には、粘着剤としての使用用途によって適宜決定される。一般的には、前記ベースポリマー１００重量部に対して、５重量部程度以下、更には０．１～５重量部配合するのが好ましい。更に、粘着剤には、必要により、前記成分のほかに、従来公知の各種の粘着付与剤、老化防止剤などの添加剤を用いてもよい。
In addition, 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. Specific examples of 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, or a melamine crosslinking agent and reacting them. When using an external cross-linking agent, 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. Furthermore, additives such as various conventionally known tackifiers and anti-aging agents may be used for the pressure-sensitive adhesive, if necessary, in addition to the above components.
粘着剤層１２は放射線硬化型粘着剤により形成することができる。放射線硬化型粘着剤は、紫外線などの放射線の照射により架橋度を増大させてその粘着力を容易に低下させることができる。
The pressure-sensitive adhesive layer 12 can be formed of a radiation curable pressure-sensitive adhesive. The radiation curable pressure-sensitive adhesive can easily reduce its adhesive strength by increasing the degree of crosslinking by irradiation with radiation such as ultraviolet rays.
放射線硬化型粘着剤は、炭素－炭素二重結合などの放射線硬化性の官能基を有し、かつ粘着性を示すものを特に制限なく使用することができる。放射線硬化型粘着剤としては、例えば、前記アクリル系粘着剤、ゴム系粘着剤などの一般的な感圧性粘着剤に、放射線硬化性のモノマー成分やオリゴマー成分を配合した添加型の放射線硬化型粘着剤を例示できる。
As the radiation curable pressure-sensitive adhesive, those having a radiation curable functional group such as a carbon-carbon double bond and exhibiting adhesiveness can be used without particular limitation. Examples of the radiation curable pressure-sensitive adhesive include an addition-type radiation curable pressure-sensitive adhesive in which a radiation-curable monomer component or oligomer component is blended with a general pressure-sensitive pressure-sensitive adhesive such as the acrylic pressure-sensitive adhesive or rubber-based pressure-sensitive adhesive. An agent can be illustrated.
配合する放射線硬化性のモノマー成分としては、例えば、ウレタンオリゴマー、ウレタン（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリストールテトラ（メタ）アクリレート、ジペンタエリストールモノヒドロキシペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレートなどが挙げられる。また放射線硬化性のオリゴマー成分はウレタン系、ポリエーテル系、ポリエステル系、ポリカーボネート系、ポリブタジエン系など種々のオリゴマーがあげられ、その分子量が１００～３００００程度の範囲のものが適当である。放射線硬化性のモノマー成分やオリゴマー成分の配合量は、前記粘着剤層の種類に応じて、粘着剤層の粘着力を低下できる量を、適宜に決定することができる。一般的には、粘着剤を構成するアクリル系ポリマーなどのベースポリマー１００重量部に対して、例えば５～５００重量部、好ましくは４０～１５０重量部程度である。
Examples of the radiation curable monomer component to be blended include urethane oligomer, urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol. Stall tetra (meth) acrylate, dipentaerystol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, and the like. Examples of the radiation 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 compounding amount of the radiation-curable monomer component or oligomer component can be appropriately determined in accordance with the type of the pressure-sensitive adhesive layer, and the amount capable of reducing the 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 a base polymer such as an acrylic polymer constituting the pressure-sensitive adhesive.
また、放射線硬化型粘着剤としては、前記説明した添加型の放射線硬化型粘着剤のほかに、ベースポリマーとして、炭素－炭素二重結合をポリマー側鎖又は主鎖中もしくは主鎖末端に有するものを用いた内在型の放射線硬化型粘着剤が挙げられる。内在型の放射線硬化型粘着剤は、低分子成分であるオリゴマー成分などを含有する必要がなく、又は多くは含まない為、経時的にオリゴマー成分などが粘着剤在中を移動することなく、安定した層構造の粘着剤層を形成することができる為好ましい。
In addition to the additive-type radiation-curable pressure-sensitive adhesive described above, the radiation-curable pressure-sensitive adhesive has a carbon-carbon double bond in the polymer side chain, main chain, or main chain terminal as a base polymer. Intrinsic radiation curable pressure sensitive adhesives using Intrinsic radiation curable adhesives do not need to contain oligomer components, which are low molecular components, or do not contain many, so the oligomer components do not move through the adhesive over time and are stable. It is preferable because an adhesive layer having a layered structure can be formed.
前記炭素－炭素二重結合を有するベースポリマーは、炭素－炭素二重結合を有し、かつ粘着性を有するものを特に制限なく使用できる。この様なベースポリマーとしては、アクリル系ポリマーを基本骨格とするものが好ましい。アクリル系ポリマーの基本骨格としては、前記例示したアクリル系ポリマーが挙げられる。
As 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. As such a base polymer, those having an acrylic polymer as a basic skeleton are preferable. Examples of the basic skeleton of the acrylic polymer include the acrylic polymers exemplified above.
前記アクリル系ポリマーへの炭素－炭素二重結合の導入法は特に制限されず、様々な方法を採用できるが、炭素－炭素二重結合はポリマー側鎖に導入するのが分子設計が容易である。例えば、予め、アクリル系ポリマーに官能基を有するモノマーを共重合した後、この官能基と反応しうる官能基及び炭素－炭素二重結合を有する化合物を、炭素－炭素二重結合の放射線硬化性を維持したまま縮合又は付加反応させる方法が挙げられる。
The method for introducing the carbon-carbon double bond into the acrylic polymer is not particularly limited, and various methods can be adopted. However, the carbon-carbon double bond can be easily introduced into the polymer side chain for easy molecular design. . For example, after a monomer having a functional group is copolymerized in advance with an acrylic polymer, a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is converted into a radiation-curable carbon-carbon double bond. A method of performing condensation or addition reaction while maintaining the above.
これら官能基の組合せの例としては、カルボン酸基とエポキシ基、カルボン酸基とアジリジル基、ヒドロキシル基とイソシアネート基などが挙げられる。これら官能基の組合せのなかでも反応追跡の容易さから、ヒドロキシル基とイソシアネート基との組合せが好適である。また、これら官能基の組み合わせにより、前記炭素－炭素二重結合を有するアクリル系ポリマーを生成するような組合せであれば、官能基はアクリル系ポリマーと前記化合物のいずれの側にあってもよいが、前記の好ましい組み合わせでは、アクリル系ポリマーがヒドロキシル基を有し、前記化合物がイソシアネート基を有する場合が好適である。この場合、炭素－炭素二重結合を有するイソシアネート化合物としては、例えば、メタクリロイルイソシアネート、２－メタクリロイルオキシエチルイソシアネート、ｍ－イソプロペニル－α，α－ジメチルベンジルイソシアネートなどが挙げられる。また、アクリル系ポリマーとしては、前記例示のヒドロキシ基含有モノマーや２－ヒドロキシエチルビニルエーテル、４－ヒドロキシブチルビニルエーテル、ジエチレングルコールモノビニルエーテルのエーテル系化合物などを共重合したものが用いられる。
Examples of combinations of these functional groups include carboxylic acid groups and epoxy groups, carboxylic acid groups and aziridyl groups, hydroxyl groups and isocyanate groups. Among these combinations of functional groups, a combination of a hydroxyl group and an isocyanate group is preferable because of easy tracking of the reaction. In addition, 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. In the preferable combination, it is preferable that the acrylic polymer has a hydroxyl group and the compound has an isocyanate group. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, and the like. As the acrylic polymer, those obtained by copolymerizing the above-mentioned exemplified hydroxy group-containing monomers, ether compounds of 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, or the like are used.
前記内在型の放射線硬化型粘着剤は、前記炭素－炭素二重結合を有するベースポリマー（特にアクリル系ポリマー）を単独で使用することができるが、特性を悪化させない程度に前記放射線硬化性のモノマー成分やオリゴマー成分を配合することもできる。放射線硬化性のオリゴマー成分などは、通常ベースポリマー１００重量部に対して３０重量部の範囲内であり、好ましくは０～１０重量部の範囲である。
As the intrinsic radiation curable pressure-sensitive adhesive, the base polymer (particularly acrylic polymer) having the carbon-carbon double bond can be used alone, but the radiation curable monomer does not deteriorate the characteristics. Components and oligomer components can also be blended. The radiation-curable oligomer component is usually in the range of 30 parts by weight, preferably in the range of 0 to 10 parts by weight, based on 100 parts by weight of the base polymer.
前記放射線硬化型粘着剤には、紫外線などにより硬化させる場合には光重合開始剤を含有させる。光重合開始剤としては、例えば、４－（２－ヒドロキシエトキシ）フェニル（２－ヒドロキシ－２－プロピル）ケトン、α－ヒドロキシ－α，α’－ジメチルアセトフェノン、２－メチル－２－ヒドロキシプロピオフェノン、１－ヒドロキシシクロヘキシルフェニルケトンなどのα－ケトール系化合物；メトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフエノン、２，２－ジエトキシアセトフェノン、２－メチル－１－［４－（メチルチオ）－フェニル］－２－モルホリノプロパン－１などのアセトフェノン系化合物；ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、アニソインメチルエーテルなどのベンゾインエーテル系化合物；ベンジルジメチルケタールなどのケタール系化合物；２－ナフタレンスルホニルクロリドなどの芳香族スルホニルクロリド系化合物；１－フェノン－１，１―プロパンジオン－２－（ｏ－エトキシカルボニル）オキシムなどの光活性オキシム系化合物；ベンゾフェノン、ベンゾイル安息香酸、３，３’－ジメチル－４－メトキシベンゾフェノンなどのベンゾフェノン系化合物；チオキサンソン、２－クロロチオキサンソン、２－メチルチオキサンソン、２，４－ジメチルチオキサンソン、イソプロピルチオキサンソン、２，４－ジクロロチオキサンソン、２，４－ジエチルチオキサンソン、２，４－ジイソプロピルチオキサンソンなどのチオキサンソン系化合物；カンファーキノン；ハロゲン化ケトン；アシルホスフィノキシド；アシルホスフォナートなどが挙げられる。光重合開始剤の配合量は、粘着剤を構成するアクリル系ポリマーなどのベースポリマー１００重量部に対して、例えば０．０５～２０重量部程度である。
The radiation curable pressure-sensitive adhesive contains a photopolymerization initiator when cured by ultraviolet rays or the like. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α'-dimethylacetophenone, 2-methyl-2-hydroxypropio Α-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-naphthalenesulfo Aromatic sulfonyl chloride compounds such as luchloride; photoactive oxime compounds such as 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime; benzophenone, benzoylbenzoic acid, 3,3′-dimethyl Benzophenone compounds such as -4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 Thioxanthone compounds such as 1,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; camphorquinone; halogenated ketone; acyl phosphinoxide; acyl phosphonate. The blending amount of the photopolymerization initiator is, for example, about 0.05 to 20 parts by weight with respect to 100 parts by weight of the base polymer such as an acrylic polymer constituting the pressure-sensitive adhesive.
また放射線硬化型粘着剤としては、例えば、特開昭６０－１９６９５６号公報に開示されている、不飽和結合を２個以上有する付加重合性化合物、エポキシ基を有するアルコキシシランなどの光重合性化合物と、カルボニル化合物、有機硫黄化合物、過酸化物、アミン、オニウム塩系化合物などの光重合開始剤とを含有するゴム系粘着剤やアクリル系粘着剤などが挙げられる。
Examples of the radiation curable pressure-sensitive adhesive include photopolymerizable compounds such as an addition polymerizable compound having two or more unsaturated bonds and an alkoxysilane having an epoxy group disclosed in JP-A-60-196956. And rubber-based pressure-sensitive adhesives and acrylic pressure-sensitive adhesives containing photopolymerization initiators such as carbonyl compounds, organic sulfur compounds, peroxides, amines, and onium salt-based compounds.
前記放射線硬化型の粘着剤層１２中には、必要に応じて、放射線照射により着色する化合物を含有させることもできる。放射線照射により、着色する化合物を粘着剤層１２に含ませることによって、放射線照射された部分のみを着色することができる。放射線照射により着色する化合物は、放射線照射前には無色又は淡色であるが、放射線照射により有色となる化合物であり、例えば、ロイコ染料などが挙げられる。放射線照射により着色する化合物の使用割合は、適宜設定できる。
In the radiation-curable pressure-sensitive adhesive layer 12, a compound that is colored by irradiation with radiation may be contained as necessary. By including a compound to be colored in the pressure-sensitive adhesive layer 12 by irradiation with radiation, only the irradiated portion can be colored. The compound that is colored by irradiation with radiation is a colorless or light color compound before irradiation with radiation, but becomes a color by irradiation with radiation, and examples thereof include leuco dyes. The use ratio of the compound colored by radiation irradiation can be set as appropriate.
（ダイシング・ダイボンドフィルム１０）
図２に示すように、ダイシング・ダイボンドフィルム１０は、ダイシングシート１と、粘着剤層１２上に配置された接着剤層３とを備える。 (Dicing die bond film 10)
As shown in FIG. 2, the dicing die-bonding film 10 includes a dicing sheet 1 and an adhesive layer 3 disposed on the pressure-sensitive adhesive layer 12.
図２に示すように、ダイシング・ダイボンドフィルム１０は、ダイシングシート１と、粘着剤層１２上に配置された接着剤層３とを備える。 (Dicing die bond film 10)
As shown in FIG. 2, the dicing die-
粘着剤層１２が、接着剤層３と接した中央部１２ａ及び中央部１２ａの周辺に配置された周辺部１２ｂを備える。中央部１２ａは、放射線照射により硬化された部分である。
The pressure-sensitive adhesive layer 12 includes a central portion 12a in contact with the adhesive layer 3 and a peripheral portion 12b arranged around the central portion 12a. The central portion 12a is a portion cured by radiation irradiation.
接着剤層３は、熱硬化性を備える。
The adhesive layer 3 has thermosetting properties.
接着剤層３のガラス転移温度は、好ましくは０℃以上、より好ましくは１０℃以上である。０℃以上であると、低温（例えば、０℃以下）環境下で接着剤層３を容易に分断できる。接着剤層３のガラス転移温度の上限は、例えば１００℃である。
The glass transition temperature of the adhesive layer 3 is preferably 0 ° C. or higher, more preferably 10 ° C. or higher. When the temperature is 0 ° C. or higher, the adhesive layer 3 can be easily divided in a low temperature (for example, 0 ° C. or lower) environment. The upper limit of the glass transition temperature of the adhesive layer 3 is, for example, 100 ° C.
接着剤層３のガラス転移温度は、アクリル樹脂のガラス転移温度などによりコントロールできる。
The glass transition temperature of the adhesive layer 3 can be controlled by the glass transition temperature of the acrylic resin.
接着剤層３は、熱可塑性樹脂を含むことが好ましい。熱可塑性樹脂としては、天然ゴム、ブチルゴム、イソプレンゴム、クロロプレンゴム、エチレン－酢酸ビニル共重合体、エチレン－アクリル酸共重合体、エチレン－アクリル酸エステル共重合体、ポリブタジエン樹脂、ポリカーボネート樹脂、熱可塑性ポリイミド樹脂、６－ナイロンや６，６－ナイロンなどのポリアミド樹脂、フェノキシ樹脂、アクリル樹脂、ＰＥＴやＰＢＴなどの飽和ポリエステル樹脂、ポリアミドイミド樹脂、又はフッ素樹脂などが挙げられる。これらの熱可塑性樹脂のうち、イオン性不純物が少なく耐熱性が高く、半導体素子の信頼性を確保できるアクリル樹脂が特に好ましい。
The adhesive layer 3 preferably contains a thermoplastic resin. Thermoplastic resins 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, thermoplasticity. Examples thereof include 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. Of these thermoplastic resins, an acrylic resin that has few ionic impurities and high heat resistance and can ensure the reliability of the semiconductor element is particularly preferable.
アクリル樹脂としては、特に限定されるものではなく、炭素数３０以下、特に炭素数４～１８の直鎖若しくは分岐のアルキル基を有するアクリル酸又はメタクリル酸のエステルの１種又は２種以上を成分とする重合体（アクリル共重合体）などが挙げられる。前記アルキル基としては、例えばメチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｔ－ブチル基、イソブチル基、アミル基、イソアミル基、ヘキシル基、へプチル基、シクロヘキシル基、２－エチルヘキシル基、オクチル基、イソオクチル基、ノニル基、イソノニル基、デシル基、イソデシル基、ウンデシル基、ラウリル基、トリデシル基、テトラデシル基、ステアリル基、オクタデシル基、又はドデシル基などが挙げられる。
The acrylic resin is not particularly limited, and one or more 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, is used as a component. And a polymer (acrylic copolymer). Examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, cyclohexyl group, 2- Examples include ethylhexyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, lauryl group, tridecyl group, tetradecyl group, stearyl group, octadecyl group, and dodecyl group.
また、重合体（アクリル共重合体）を形成する他のモノマーとしては、特に限定されるものではなく、例えばアクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマール酸若しくはクロトン酸などの様なカルボキシル基含有モノマー、無水マレイン酸若しくは無水イタコン酸などの様な酸無水物モノマー、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸６－ヒドロキシヘキシル、（メタ）アクリル酸８－ヒドロキシオクチル、（メタ）アクリル酸１０－ヒドロキシデシル、（メタ）アクリル酸１２－ヒドロキシラウリル若しくは（４－ヒドロキシメチルシクロヘキシル）－メチルアクリレートなどの様なヒドロキシル基含有モノマー、スチレンスルホン酸、アリルスルホン酸、２－（メタ）アクリルアミド－２－メチルプロパンスルホン酸、（メタ）アクリルアミドプロパンスルホン酸、スルホプロピル（メタ）アクリレート若しくは（メタ）アクリロイルオキシナフタレンスルホン酸などの様なスルホン酸基含有モノマー、又は２－ヒドロキシエチルアクリロイルホスフェートなどの様な燐酸基含有モノマーが挙げられる。
In addition, the other monomer forming the polymer (acrylic copolymer) is not particularly limited, and for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid Or a carboxyl group-containing monomer such as crotonic acid, an acid anhydride monomer such as maleic anhydride or itaconic anhydride, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth ) 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate or (4 -Hydroxymethyl cycle Hexyl) -hydroxyl group-containing monomers such as methyl acrylate, styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate Alternatively, a sulfonic acid group-containing monomer such as (meth) acryloyloxynaphthalene sulfonic acid, or a phosphoric acid group-containing monomer such as 2-hydroxyethylacryloyl phosphate can be used.
アクリル樹脂のなかでも、重量平均分子量が１０万以上のものが好ましく、３０万～３００万のものがより好ましく、５０万～２００万のものがさらに好ましい。上記数値範囲内であると、接着性及び耐熱性に優れるからである。なお、重量平均分子量は、ＧＰＣ（ゲル・パーミエーション・クロマトグラフィー）により測定し、ポリスチレン換算により算出された値である。
Among the acrylic resins, those having a weight average molecular weight of 100,000 or more are preferable, those having 300,000 to 3,000,000 are more preferable, and those having 500,000 to 2,000,000 are more preferable. It is because it is excellent in adhesiveness and heat resistance in the said numerical range. The weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
接着剤層３は、熱硬化性樹脂を含むことが好ましい。これにより、熱安定性を向上できる。
The adhesive layer 3 preferably contains a thermosetting resin. Thereby, thermal stability can be improved.
熱硬化性樹脂としては、フェノール樹脂、アミノ樹脂、不飽和ポリエステル樹脂、エポキシ樹脂、ポリウレタン樹脂、シリコーン樹脂、又は熱硬化性ポリイミド樹脂などが挙げられる。特に、半導体素子を腐食させるイオン性不純物などの含有が少ないエポキシ樹脂が好ましい。また、エポキシ樹脂の硬化剤としてはフェノール樹脂が好ましい。
Examples of the thermosetting resin include phenol resin, amino resin, unsaturated polyester resin, epoxy resin, polyurethane resin, silicone resin, and thermosetting polyimide resin. In particular, an epoxy resin containing a small amount of ionic impurities that corrode semiconductor elements is preferable. Moreover, as a hardening | curing agent of an epoxy resin, a phenol resin is preferable.
エポキシ樹脂としては特に限定されず、例えばビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＳ型、臭素化ビスフェノールＡ型、水添ビスフェノールＡ型、ビスフェノールＡＦ型、ビフェニル型、ナフタレン型、フルオンレン型、フェノールノボラック型、オルソクレゾールノボラック型、トリスヒドロキシフェニルメタン型、テトラフェニロールエタン型などの二官能エポキシ樹脂や多官能エポキシ樹脂、又はヒダントイン型、トリスグリシジルイソシアヌレート型若しくはグリシジルアミン型などのエポキシ樹脂が用いられる。これらのエポキシ樹脂のうちノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリスヒドロキシフェニルメタン型樹脂又はテトラフェニロールエタン型エポキシ樹脂が特に好ましい。これらのエポキシ樹脂は、硬化剤としてのフェノール樹脂との反応性に富み、耐熱性などに優れるからである。
The epoxy resin is not particularly limited. 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 novolac type. Bifunctional epoxy resins such as ortho-cresol novolak type, trishydroxyphenylmethane type, tetraphenylolethane type, etc., and epoxy resins such as hydantoin type, trisglycidyl isocyanurate type, or glycidylamine type are used. Of these 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.
フェノール樹脂は、エポキシ樹脂の硬化剤として作用するものであり、例えば、フェノールノボラック樹脂、フェノールアラルキル樹脂、クレゾールノボラック樹脂、ｔｅｒｔ－ブチルフェノールノボラック樹脂、ノニルフェノールノボラック樹脂などのノボラック型フェノール樹脂、レゾール型フェノール樹脂、ポリパラオキシスチレンなどのポリオキシスチレンなどが挙げられる。これらのフェノール樹脂のうちフェノールノボラック樹脂、フェノールアラルキル樹脂が特に好ましい。半導体装置の接続信頼性を向上させることができるからである。
The phenol resin acts as a curing agent for the epoxy resin. For example, a novolac type phenol resin such as a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a tert-butylphenol novolak resin, a nonylphenol novolak resin, or a resol type phenol resin. And polyoxystyrene such as polyparaoxystyrene. 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.
エポキシ樹脂とフェノール樹脂との配合割合は、例えば、エポキシ樹脂成分中のエポキシ基１当量当たりフェノール樹脂中の水酸基が０．５～２．０当量になるように配合することが好適である。より好適なのは、０．８～１．２当量である。即ち、両者の配合割合が前記範囲を外れると、十分な硬化反応が進まず、硬化物の特性が劣化し易くなるからである。
The mixing 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 product are likely to deteriorate.
接着剤層３がエポキシ樹脂、フェノール樹脂及びアクリル樹脂を含む場合、アクリル樹脂１００重量部に対して、エポキシ樹脂及びフェノール樹脂の合計含有量は、好ましくは１００重量部～１３００重量部である。
When the adhesive layer 3 contains an epoxy resin, a phenol resin, and an acrylic resin, the total content of the epoxy resin and the phenol resin is preferably 100 parts by weight to 1300 parts by weight with respect to 100 parts by weight of the acrylic resin.
接着剤層３を予めある程度架橋をさせておく場合には、作製に際し、重合体の分子鎖末端の官能基等と反応する多官能性化合物を架橋剤として添加させておくのがよい。これにより、高温下での接着特性を向上させ、耐熱性の改善を図ることができる。
When the adhesive layer 3 is previously crosslinked to some extent, it is preferable to add a polyfunctional compound that reacts with a functional group at the molecular chain end of the polymer as a crosslinking agent. Thereby, the adhesive property under high temperature can be improved and heat resistance can be improved.
架橋剤としては、従来公知のものを採用することができる。特に、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ｐ－フェニレンジイソシアネート、１，５－ナフタレンジイソシアネート、多価アルコールとジイソシアネートの付加物等のポリイソシアネート化合物がより好ましい。架橋剤の添加量としては、重合体１００重量部に対し、通常０．０５～７重量部とするのが好ましい。架橋剤の量が７重量部より多いと、接着力が低下するので好ましくない。その一方、０．０５重量部より少ないと、凝集力が不足するので好ましくない。また、この様なポリイソシアネート化合物と共に、必要に応じて、エポキシ樹脂等の他の多官能性化合物を一緒に含ませるようにしてもよい。
A conventionally well-known thing can be employ | adopted as a crosslinking agent. 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 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.
また、接着剤層３には、その用途に応じて無機充填剤を適宜配合することができる。無機充填剤の配合は、導電性の付与や熱伝導性の向上、弾性率の調節等を可能とする。無機充填剤としては、例えば、シリカ、クレー、石膏、炭酸カルシウム、硫酸バリウム、酸化アルミナ、酸化ベリリウム、炭化珪素、窒化珪素等のセラミック類、アルミニウム、銅、銀、金、ニッケル、クロム、鉛、錫、亜鉛、パラジウム、半田等の金属、又は合金類、その他カーボン等からなる種々の無機粉末が挙げられる。
Further, an inorganic filler can be appropriately blended in the adhesive layer 3 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. Examples of inorganic fillers 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, lead, Examples thereof include various inorganic powders made of metals such as tin, zinc, palladium, solder, or alloys, and other carbon.
接着剤層３は、熱硬化触媒を含むことが好ましい。熱硬化触媒の含有量は、アクリル樹脂１００重量部に対し０．０１～３重量部が好ましく、０．０５～１重量部がより好ましい。
The adhesive layer 3 preferably contains a thermosetting catalyst. The content of the thermosetting catalyst is preferably 0.01 to 3 parts by weight and more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the acrylic resin.
熱硬化触媒としては特に限定されず、例えば、イミダゾール系化合物、トリフェニルフォスフィン系化合物、アミン系化合物、トリフェニルボラン系化合物、トリハロゲンボラン系化合物等が挙げられる。
The thermosetting catalyst is not particularly limited, and examples thereof include imidazole compounds, triphenylphosphine compounds, amine compounds, triphenylborane compounds, and trihalogenborane compounds.
イミダゾール系化合物としては、２－メチルイミダゾール（商品名；２ＭＺ）、２－ウンデシルイミダゾール（商品名；Ｃ１１Ｚ）、２－ヘプタデシルイミダゾール（商品名；Ｃ１７Ｚ）、１,２－ジメチルイミダゾール（商品名；１．２ＤＭＺ）、２－エチル－４－メチルイミダゾール（商品名；２Ｅ４ＭＺ）、２－フェニルイミダゾール（商品名；２ＰＺ）、２－フェニル－４－メチルイミダゾール（商品名；２Ｐ４ＭＺ）、１－ベンジル－２－メチルイミダゾール（商品名；１Ｂ２ＭＺ）、１－ベンジル－２－フェニルイミダゾール（商品名；１Ｂ２ＰＺ）、１－シアノエチル－２－メチルイミダゾール（商品名；２ＭＺ－ＣＮ）、１－シアノエチル－２－ウンデシルイミダゾール（商品名；Ｃ１１Ｚ－ＣＮ）、１－シアノエチル－２－フェニルイミダゾリウムトリメリテイト（商品名；２ＰＺＣＮＳ－ＰＷ）、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン（商品名；２ＭＺ－Ａ）、２，４－ジアミノ－６－［２’－ウンデシルイミダゾリル－（１’）］－エチル－ｓ－トリアジン（商品名；Ｃ１１Ｚ－Ａ）、２，４－ジアミノ－６－［２’－エチル－４’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン（商品名；２Ｅ４ＭＺ－Ａ）、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジンイソシアヌル酸付加物（商品名；２ＭＡ－ＯＫ）、２－フェニル－４，５－ジヒドロキシメチルイミダゾール（商品名；２ＰＨＺ－ＰＷ）、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール（商品名；２Ｐ４ＭＨＺ－ＰＷ）等が挙げられる（いずれも四国化成（株）製）。
Examples of imidazole compounds include 2-methylimidazole (trade name; 2MZ), 2-undecylimidazole (trade name; C11Z), 2-heptadecylimidazole (trade name; C17Z), and 1,2-dimethylimidazole (trade name). 1.2DMZ), 2-ethyl-4-methylimidazole (trade name; 2E4MZ), 2-phenylimidazole (trade name; 2PZ), 2-phenyl-4-methylimidazole (trade name; 2P4MZ), 1-benzyl -2-Methylimidazole (trade name; 1B2MZ), 1-benzyl-2-phenylimidazole (trade name; 1B2PZ), 1-cyanoethyl-2-methylimidazole (trade name; 2MZ-CN), 1-cyanoethyl-2- Undecylimidazole (trade name; C11Z-CN), 1-cyanoethyl-2 -Phenylimidazolium trimellitate (trade name; 2PZCNS-PW), 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine (trade name; 2MZ-A) 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine (trade name; C11Z-A), 2,4-diamino-6- [2′-ethyl -4'-methylimidazolyl- (1 ')]-ethyl-s-triazine (trade name; 2E4MZ-A), 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl- s-Triazine isocyanuric acid adduct (trade name; 2MA-OK), 2-phenyl-4,5-dihydroxymethylimidazole (trade name; 2PHZ-PW), 2-phenyl-4-methyl-5-hydroxy Methylimidazole (trade name; 2P4MHZ-PW), and the like (all made by Shikoku Kasei Co., Ltd.).
トリフェニルフォスフィン系化合物としては特に限定されず、例えば、トリフェニルフォスフィン、トリブチルフォスフィン、トリ（ｐ－メチルフェニル）フォスフィン、トリ（ノニルフェニル）フォスフィン、ジフェニルトリルフォスフィン等のトリオルガノフォスフィン、テトラフェニルホスホニウムブロマイド（商品名；ＴＰＰ－ＰＢ）、メチルトリフェニルホスホニウム（商品名；ＴＰＰ－ＭＢ）、メチルトリフェニルホスホニウムクロライド（商品名；ＴＰＰ－ＭＣ）、メトキシメチルトリフェニルホスホニウム（商品名；ＴＰＰ－ＭＯＣ）、ベンジルトリフェニルホスホニウムクロライド（商品名；ＴＰＰ－ＺＣ）等が挙げられる（いずれも北興化学社製）。
The triphenylphosphine compound is not particularly limited, and examples thereof include triorganophosphine such as triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, and diphenyltolylphosphine. , Tetraphenylphosphonium bromide (trade name; TPP-PB), methyltriphenylphosphonium (trade name; TPP-MB), methyltriphenylphosphonium chloride (trade name; TPP-MC), methoxymethyltriphenylphosphonium (trade name; TPP-MOC), benzyltriphenylphosphonium chloride (trade name: TPP-ZC), etc. (all manufactured by Hokuko Chemical Co., Ltd.).
トリフェニルボラン系化合物としては特に限定されず、例えば、トリ（ｐ－メチルフェニル）フォスフィン等が挙げられる。また、トリフェニルボラン系化合物としては、更にトリフェニルフォスフィン構造を有するものも含まれる。当該トリフェニルフォスフィン構造及びトリフェニルボラン構造を有する化合物としては特に限定されず、例えば、テトラフェニルホスホニウムテトラフェニルボレート（商品名；ＴＰＰ－Ｋ）、テトラフェニルホスホニウムテトラ－ｐ－トリボレート（商品名；ＴＰＰ－ＭＫ）、ベンジルトリフェニルホスホニウムテトラフェニルボレート（商品名；ＴＰＰ－ＺＫ）、トリフェニルホスフィントリフェニルボラン（商品名；ＴＰＰ－Ｓ）等が挙げられる（いずれも北興化学社製）。
The triphenylborane compound is not particularly limited, and examples thereof include tri (p-methylphenyl) phosphine. The triphenylborane compound further includes those having a triphenylphosphine structure. The compound having the triphenylphosphine structure and the triphenylborane structure is not particularly limited. For example, tetraphenylphosphonium tetraphenylborate (trade name; TPP-K), tetraphenylphosphonium tetra-p-triborate (trade name; TPP-MK), benzyltriphenylphosphonium tetraphenylborate (trade name; TPP-ZK), triphenylphosphine triphenylborane (trade name; TPP-S), and the like (all manufactured by Hokuko Chemical Co., Ltd.).
アミノ系化合物としては特に限定されず、例えば、モノエタノールアミントリフルオロボレート（ステラケミファ（株）製）、ジシアンジアミド（ナカライテスク（株）製）等が挙げられる。
The amino compound is not particularly limited, and examples thereof include monoethanolamine trifluoroborate (manufactured by Stella Chemifa Corporation), dicyandiamide (manufactured by Nacalai Tesque Corporation), and the like.
トリハロゲンボラン系化合物としては特に限定されず、例えば、トリクロロボラン等が挙げられる。
The trihalogen borane-based compound is not particularly limited, and examples thereof include trichloroborane.
なお、接着剤層３には、必要に応じて他の添加剤を適宜に配合することができる。他の添加剤としては、例えば難燃剤、シランカップリング剤又はイオントラップ剤等が挙げられる。難燃剤としては、例えば、三酸化アンチモン、五酸化アンチモン、臭素化エポキシ樹脂等が挙げられる。シランカップリング剤としては、例えば、β－（３、４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン等が挙げられる。イオントラップ剤としては、例えばハイドロタルサイト類、水酸化ビスマス等が挙げられる。
In addition, other additives can be appropriately blended in the adhesive layer 3 as necessary. Examples of other additives include flame retardants, silane coupling agents, ion trapping agents, and the like. Examples of the flame retardant include antimony trioxide, antimony pentoxide, brominated epoxy resin, and the like. Examples of the silane coupling agent include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and the like. Examples of the ion trapping agent include hydrotalcites and bismuth hydroxide.
接着剤層３は、通常の方法で製造できる。例えば、前記各成分を含有する接着剤組成物溶液を作製し、接着剤組成物溶液を基材セパレータ上に所定厚みとなる様に塗布して塗布膜を形成した後、該塗布膜を乾燥させることで、接着剤層３を製造できる。
The adhesive layer 3 can be manufactured by a usual method. For example, an adhesive composition solution containing each of the above components is prepared, and the adhesive composition solution is applied on a base separator so as to have a predetermined thickness to form a coating film, and then the coating film is dried. Thus, the adhesive layer 3 can be manufactured.
接着剤組成物溶液に用いる溶媒としては特に限定されないが、前記各成分を均一に溶解、混練又は分散できる有機溶媒が好ましい。例えば、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ-メチルピロリドン、アセトン、メチルエチルケトン、シクロヘキサノンなどのケトン系溶媒、トルエン、キシレンなどが挙げられる。塗布方法は特に限定されない。溶剤塗工の方法としては、例えば、ダイコーター、グラビアコーター、ロールコーター、リバースコーター、コンマコーター、パイプドクターコーター、スクリーン印刷などが挙げられる。なかでも、塗布厚みの均一性が高いという点から、ダイコーターが好ましい。
The solvent used in the adhesive composition solution is not particularly limited, but an organic solvent capable of uniformly dissolving, kneading or dispersing the above components is preferable. Examples thereof include ketone solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone, and cyclohexanone, toluene, xylene, and the like. The application method is not particularly limited. Examples of the solvent coating method include a die coater, a gravure coater, a roll coater, a reverse coater, a comma coater, a pipe doctor coater, and screen printing. Of these, a die coater is preferable in terms of high uniformity of coating thickness.
基材セパレータとしては、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレン、ポリプロピレンや、フッ素系剥離剤、長鎖アルキルアクリレート系剥離剤などの剥離剤により表面コートされたプラスチックフィルムや紙などが使用可能である。接着剤組成物溶液の塗布方法としては、例えば、ロール塗工、スクリーン塗工、グラビア塗工などが挙げられる。また、塗布膜の乾燥条件は特に限定されず、例えば、乾燥温度７０～１６０℃、乾燥時間１～５分間で行うことができる。
As the base material separator, polyethylene terephthalate (PET), polyethylene, 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 can be used. Examples of the method for applying the adhesive composition solution include roll coating, screen coating, and gravure coating. The drying conditions for the coating film are not particularly limited, and for example, the drying can be performed at a drying temperature of 70 to 160 ° C. and a drying time of 1 to 5 minutes.
接着剤層３の製造方法としては、例えば、前記各成分をミキサーにて混合し、得られた混合物をプレス成形して接着剤層３を製造する方法なども好適である。ミキサーとしてはプラネタリーミキサーなどが挙げられる。
As a method for producing the adhesive layer 3, for example, a method of producing the adhesive layer 3 by mixing the respective components with a mixer and press-molding the obtained mixture is also suitable. A planetary mixer etc. are mentioned as a mixer.
接着剤層３の厚みは特に限定されないが、５μｍ以上が好ましく、１５μｍ以上がより好ましい。接着剤層３の厚みは１００μｍ以下が好ましく、５０μｍ以下がより好ましい。
The thickness of the adhesive layer 3 is not particularly limited, but is preferably 5 μm or more, and more preferably 15 μm or more. The thickness of the adhesive layer 3 is preferably 100 μm or less, and more preferably 50 μm or less.
接着剤層３は、リードフレームなどの被着体と半導体素子とを接着するダイアタッチフィルムとして使用できる。被着体としては、リードフレーム、インターポーザ、半導体素子などが挙げられる。
The adhesive layer 3 can be used as a die attach film for bonding an adherend such as a lead frame and a semiconductor element. Examples of the adherend include a lead frame, an interposer, and a semiconductor element.
接着剤層３は、セパレータにより保護されていることが好ましい（図示せず）。セパレータは、実用に供するまで接着剤層３を保護する保護材としての機能を有している。セパレータは、接着剤層３に半導体ウエハを貼着する際に剥がされる。セパレータとしては、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレン、ポリプロピレンや、フッ素系剥離剤、長鎖アルキルアクリレート系剥離剤などの剥離剤により表面コートされたプラスチックフィルムや紙なども使用可能である。
The adhesive layer 3 is preferably protected by a separator (not shown). The separator has a function as a protective material that protects the adhesive layer 3 until it is put to practical use. The separator is peeled off when the semiconductor wafer is attached to the adhesive layer 3. As the separator, it is also possible to use polyethylene terephthalate (PET), polyethylene, polypropylene, a plastic film or paper whose surface is coated with a release agent such as a fluorine release agent or a long-chain alkyl acrylate release agent.
ダイシング・ダイボンドフィルム１０は、通常の方法で製造できる。例えば、ダイシングシート１と接着剤層３とを貼り合わせることで、ダイシング・ダイボンドフィルム１０を製造できる。
The dicing die bond film 10 can be manufactured by a normal method. For example, the dicing die-bonding film 10 can be manufactured by bonding the dicing sheet 1 and the adhesive layer 3 together.
ダイシング・ダイボンドフィルム１０は、半導体装置を製造するために使用できる。
The dicing die bond film 10 can be used for manufacturing a semiconductor device.
（半導体装置の製造方法）
図３に示すように、半導体ウエハ４Ｐの内部に集光点を合わせ、格子状の分割予定ライン４Ｌに沿ってレーザー光１００を照射し、半導体ウエハ４Ｐの内部に改質領域４１を形成する。これにより、分割ウエハ４を得る。 (Method for manufacturing semiconductor device)
As shown in FIG. 3, the condensing point is aligned inside thesemiconductor wafer 4P, and the laser beam 100 is irradiated along the lattice-shaped division planned line 4L, thereby forming the modified region 41 inside the semiconductor wafer 4P. Thereby, the divided wafer 4 is obtained.
図３に示すように、半導体ウエハ４Ｐの内部に集光点を合わせ、格子状の分割予定ライン４Ｌに沿ってレーザー光１００を照射し、半導体ウエハ４Ｐの内部に改質領域４１を形成する。これにより、分割ウエハ４を得る。 (Method for manufacturing semiconductor device)
As shown in FIG. 3, the condensing point is aligned inside the
レーザー光１００の照射条件は、例えば、以下の条件の範囲内で適宜調整できる。
（Ａ）レーザー光１００
レーザー光源 半導体レーザー励起Ｎｄ：ＹＡＧレーザー
波長 １０６４ｎｍ
レーザー光スポット断面積 ３．１４×１０－８ｃｍ２
発振形態 Ｑスイッチパルス
繰り返し周波数 １００ｋＨｚ以下
パルス幅 １μｓ以下
出力 １ｍＪ以下
レーザー光品質 ＴＥＭ００
偏光特性 直線偏光
（Ｂ）集光用レンズ
倍率 １００倍以下
ＮＡ ０．５５
レーザー光波長に対する透過率 １００％以下
（Ｃ）半導体ウエハが載置される裁置台の移動速度 ２８０ｍｍ／秒以下 The irradiation conditions of thelaser beam 100 can be adjusted as appropriate within the range of the following conditions, for example.
(A)Laser beam 100
Laser light source Semiconductor laser pumped Nd: YAG laser Wavelength 1064nm
Laser light spot cross section 3.14 × 10 −8 cm 2
Oscillation form Q switchpulse Repetition frequency 100 kHz or less Pulse width 1 μs or less Output 1 mJ or less Laser light quality TEM00
Polarization characteristics Linearly polarized light (B)Condensing lens Magnification 100 times or less NA 0.55
Transmittance with respect to laser light wavelength: 100% or less (C) Moving speed of placing table on which semiconductor wafer is placed 280 mm / second or less
（Ａ）レーザー光１００
レーザー光源 半導体レーザー励起Ｎｄ：ＹＡＧレーザー
波長 １０６４ｎｍ
レーザー光スポット断面積 ３．１４×１０－８ｃｍ２
発振形態 Ｑスイッチパルス
繰り返し周波数 １００ｋＨｚ以下
パルス幅 １μｓ以下
出力 １ｍＪ以下
レーザー光品質 ＴＥＭ００
偏光特性 直線偏光
（Ｂ）集光用レンズ
倍率 １００倍以下
ＮＡ ０．５５
レーザー光波長に対する透過率 １００％以下
（Ｃ）半導体ウエハが載置される裁置台の移動速度 ２８０ｍｍ／秒以下 The irradiation conditions of the
(A)
Laser light source Semiconductor laser pumped Nd: YAG laser Wavelength 1064nm
Laser light spot cross section 3.14 × 10 −8 cm 2
Oscillation form Q switch
Polarization characteristics Linearly polarized light (B)
Transmittance with respect to laser light wavelength: 100% or less (C) Moving speed of placing table on which semiconductor wafer is placed 280 mm / second or less
なお、レーザー光１００の照射により改質領域４１を形成する方法については、特許第３４０８８０５号公報、特開２００３－３３８５６７号公報などに詳述されているので、ここでの詳細な説明は省略することとする。
The method for forming the modified region 41 by irradiation with the laser beam 100 is described in detail in Japanese Patent No. 3408805, Japanese Patent Application Laid-Open No. 2003-338567, and the like, and detailed description thereof is omitted here. I will do it.
図４に示すように、分割ウエハ４が、改質領域４１を備える。分割ウエハ４が、半導体素子５Ａ、５Ｂ、５Ｃ、……、５Ｈをさらに備える。
As shown in FIG. 4, the divided wafer 4 includes a modified region 41. The divided wafer 4 further includes semiconductor elements 5A, 5B, 5C,.
分割ウエハ４は、表面（おもてめん）、及び表面に対向した裏面で両面が定義される。表面は、回路が設けられた面である。一方、裏面は、回路が設けられていない面である。
As for the divided wafer 4, both sides are defined by the front surface (Otemen) and the back surface facing the front surface. The surface is a surface on which a circuit is provided. On the other hand, the back surface is a surface on which no circuit is provided.
分割ウエハ４の裏面を研削して、分割ウエハ４を薄くする。
The back surface of the divided wafer 4 is ground to make the divided wafer 4 thinner.
図５に示すように、接着剤層３に分割ウエハ４を圧着して、積層体２１を得る。積層体２１は、ダイシング・ダイボンドフィルム１０及び接着剤層３上に配置された分割ウエハ４を備える。
As shown in FIG. 5, the divided wafer 4 is pressure-bonded to the adhesive layer 3 to obtain a laminate 21. The laminate 21 includes the dicing die bond film 10 and the divided wafer 4 disposed on the adhesive layer 3.
図６に示すように、周辺部１２ｂにダイシングリング３１を貼り付ける。
As shown in FIG. 6, a dicing ring 31 is attached to the peripheral portion 12b.
図７に示すように、積層体２１の下方に配置された突き上げ部３３を上昇させることによりダイシングシート１を拡張し、改質領域４１を起点に分割ウエハ４及び接着剤層３を分断する。これにより、ダイシングシート１及び粘着剤層１２上に配置されたダイボンド用チップ２Ａ、２Ｂ、２Ｃ、……、２Ｈを備える分割構造体５１を得る。ダイボンド用チップ２Ａは、接着フィルム２２Ａ及び接着フィルム２２Ａ上に配置された半導体素子５Ａを備える。ダイボンド用チップ２Ｂは、接着フィルム２２Ｂ及び接着フィルム２２Ｂ上に配置された半導体素子５Ｂを備える。ダイボンド用チップ２Ｃは、接着フィルム２２Ｃ及び接着フィルム２２Ｃ上に配置された半導体素子５Ｃを備える。ダイボンド用チップ２Ｄは、接着フィルム２２Ｄ及び接着フィルム２２Ｄ上に配置された半導体素子５Ｄを備える。ダイボンド用チップ２Ｅは、接着フィルム２２Ｅ及び接着フィルム２２Ｅ上に配置された半導体素子５Ｅを備える。ダイボンド用チップ２Ｆは、接着フィルム２２Ｆ及び接着フィルム２２Ｆ上に配置された半導体素子５Ｆを備える。ダイボンド用チップ２Ｇは、接着フィルム２２Ｇ及び接着フィルム２２Ｇ上に配置された半導体素子５Ｇを備える。ダイボンド用チップ２Ｈは、接着フィルム２２Ｈ及び接着フィルム２２Ｈ上に配置された半導体素子５Ｈを備える。接着フィルム２２Ａ、２２Ｂ、２２Ｃ、……、２２Ｈが粘着剤層１２と接する。
As shown in FIG. 7, the dicing sheet 1 is expanded by raising the push-up portion 33 disposed below the laminated body 21, and the divided wafer 4 and the adhesive layer 3 are divided from the modified region 41 as a starting point. Thereby, the division | segmentation structure 51 provided with chip | tip 2A, 2B, 2C, ..., 2H for die bonding arrange | positioned on the dicing sheet 1 and the adhesive layer 12 is obtained. The die bonding chip 2A includes an adhesive film 22A and a semiconductor element 5A disposed on the adhesive film 22A. The die bonding chip 2B includes an adhesive film 22B and a semiconductor element 5B arranged on the adhesive film 22B. The die bonding chip 2C includes an adhesive film 22C and a semiconductor element 5C disposed on the adhesive film 22C. The die bonding chip 2D includes an adhesive film 22D and a semiconductor element 5D arranged on the adhesive film 22D. The die bonding chip 2E includes an adhesive film 22E and a semiconductor element 5E disposed on the adhesive film 22E. The die-bonding chip 2F includes an adhesive film 22F and a semiconductor element 5F disposed on the adhesive film 22F. The die-bonding chip 2G includes an adhesive film 22G and a semiconductor element 5G disposed on the adhesive film 22G. The die bonding chip 2H includes an adhesive film 22H and a semiconductor element 5H disposed on the adhesive film 22H. The adhesive films 22A, 22B, 22C,..., 22H are in contact with the pressure-sensitive adhesive layer 12.
好ましくは、ダイシングシート１を１０℃以下で拡張する。より好ましくは、０℃以下で拡張する。０℃以下であると、接着剤層３を容易に分断できる。温度の下限は特に限定されず、例えば、－２０℃である。
Preferably, the dicing sheet 1 is expanded at 10 ° C. or lower. More preferably, the expansion is performed at 0 ° C. or less. The adhesive bond layer 3 can be parted easily as it is 0 degrees C or less. The lower limit of the temperature is not particularly limited, and is −20 ° C., for example.
突き上げ部３３が上昇する速度は、好ましくは０．１ｍｍ／秒以上、より好ましくは１ｍｍ／秒以上である。０．１ｍｍ／秒以上であると、容易に分断できる。一方、エキスパンド速度の上限は特に限定されない。
The speed at which the push-up portion 33 rises is preferably 0.1 mm / second or more, more preferably 1 mm / second or more. If it is 0.1 mm / second or more, it can be easily divided. On the other hand, the upper limit of the expanding speed is not particularly limited.
図８に示すように、突き上げ部３３を下降させる。突き上げ部３３を下降させることにより、周辺部１２ｂにたるみが生じる。
As shown in FIG. 8, the push-up portion 33 is lowered. When the push-up portion 33 is lowered, sagging occurs in the peripheral portion 12b.
図９に示すように、分割構造体５１の下方に配置された吸着テーブル３２を上昇させることによりダイシングシート１を拡張し、拡張を維持しながら吸着テーブル３２でダイシングシート１を吸引する。
As shown in FIG. 9, the dicing sheet 1 is expanded by raising the suction table 32 arranged below the divided structure 51, and the dicing sheet 1 is sucked by the suction table 32 while maintaining the expansion.
図１０に示すように、吸着テーブル３２でダイシングシート１を吸引しながら、吸着テーブル３２を下降させる。
As shown in FIG. 10, the suction table 32 is lowered while the dicing sheet 1 is sucked by the suction table 32.
吸着テーブル３２でダイシングシート１を吸引しながら、周辺部１２ｂに熱風を当てる。周辺部１２ｂに熱風を当てることによりたるみを取り除くことが可能で、ダイボンド用チップ２Ａとダイボンド用チップ２Ｂ、ダイボンド用チップ２Ｂとダイボンド用チップ２Ｃ、……ダイボンド用チップ２Ｇとダイボンド用チップ２Ｈの接触を防止できる。
While sucking the dicing sheet 1 with the suction table 32, hot air is applied to the peripheral portion 12b. It is possible to remove slack by applying hot air to the peripheral portion 12b, and contact between the die bonding chip 2A and the die bonding chip 2B, the die bonding chip 2B and the die bonding chip 2C, ..., the contact between the die bonding chip 2G and the die bonding chip 2H Can be prevented.
熱風の温度は、好ましくは２２０℃以上、より好ましくは２５０℃以上である。２２０℃以上であると、周辺部１２ｂを容易に収縮させることができる。一方、熱風の温度は、好ましくは４００℃以下、より好ましくは３００℃以下で熱する。４００℃以下であると、ダイシングシート１の破損を防止できる。
The temperature of the hot air is preferably 220 ° C. or higher, more preferably 250 ° C. or higher. The peripheral part 12b can be easily contracted as it is 220 degreeC or more. On the other hand, the hot air is heated at a temperature of preferably 400 ° C. or lower, more preferably 300 ° C. or lower. When the temperature is 400 ° C. or lower, the dicing sheet 1 can be prevented from being damaged.
次いで、粘着剤層１２が紫外線硬化型である場合は、粘着剤層１２に紫外線を照射して、粘着剤層１２を硬化させる。これにより、粘着剤層１２のダイボンド用チップ２に対する粘着力を低下させることができる。紫外線照射の際の照射強度、照射時間などの条件は特に限定されず、適宜必要に応じて設定すればよい。粘着剤層１２が紫外線硬化型でない場合は、粘着剤層１２に紫外線を照射する必要はない。
Next, when the pressure-sensitive adhesive layer 12 is an ultraviolet curable type, the pressure-sensitive adhesive layer 12 is cured by irradiating the pressure-sensitive adhesive layer 12 with ultraviolet rays. Thereby, the adhesive force with respect to the chip | tip 2 for die-bonding of the adhesive layer 12 can be reduced. Conditions such as irradiation intensity and irradiation time at the time of ultraviolet irradiation are not particularly limited, and may be set as necessary. When the pressure-sensitive adhesive layer 12 is not an ultraviolet curable type, it is not necessary to irradiate the pressure-sensitive adhesive layer 12 with ultraviolet rays.
ダイボンド用チップ２Ａをピックアップする。ピックアップの方法としては特に限定されず、従来公知の種々の方法を採用できる。例えば、ダイボンド用チップ２Ａをニードルによって突き上げ、突き上げられたダイボンド用チップ２Ａをピックアップ装置によってピックアップする方法などが挙げられる。
Pick up die bonding chip 2A. The pickup method is not particularly limited, and various conventionally known methods can be employed. For example, there is a method of pushing up the die bonding chip 2A with a needle and picking up the pushed up die bonding chip 2A with a pickup device.
図１１に示すように、ダイボンド用チップ２Ａを被着体６に圧着して、半導体素子付き被着体６１を得る。半導体素子付き被着体６１は、被着体６、被着体６上に配置された接着フィルム２２Ａ及び接着フィルム２２Ａ上に配置された半導体素子５Ａを備える。
As shown in FIG. 11, the die bonding chip 2A is pressure-bonded to the adherend 6 to obtain an adherend 61 with a semiconductor element. The adherend 61 with a semiconductor element includes an adherend 6, an adhesive film 22 </ b> A disposed on the adherend 6, and a semiconductor element 5 </ b> A disposed on the adhesive film 22 </ b> A.
圧着温度は、好ましくは８０℃以上、より好ましくは９０℃以上である。また、圧着温度は、好ましくは１５０℃以下、より好ましくは１３０℃以下である。
The crimping temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher. The pressure bonding temperature is preferably 150 ° C. or lower, more preferably 130 ° C. or lower.
続いて、半導体素子付き被着体６１を加熱することにより接着フィルム２２Ａを熱硬化させて、半導体素子５Ａを被着体６に固着させる。
Subsequently, by heating the adherend 61 with a semiconductor element, the adhesive film 22A is thermally cured, and the semiconductor element 5A is fixed to the adherend 6.
なお、半導体素子付き被着体６１を加圧下で加熱することにより接着フィルム２２Ａを熱硬化させることが好ましい。加圧下で接着フィルム２２Ａを熱硬化させることにより、接着フィルム２２Ａと被着体６との間に存在するボイドを容易に消滅させることができる。
In addition, it is preferable to thermally cure the adhesive film 22A by heating the adherend 61 with a semiconductor element under pressure. By thermally curing the adhesive film 22A under pressure, voids existing between the adhesive film 22A and the adherend 6 can be easily eliminated.
加圧下で加熱する方法としては、例えば、不活性ガスが充填されたチャンバー内に配置された半導体素子付き被着体６１を加熱する方法などが挙げられる。
加圧雰囲気の圧力は、好ましくは０．５ｋｇ／ｃｍ２（４．９×１０－２ＭＰａ）以上、より好ましくは１ｋｇ／ｃｍ２（９．８×１０－２ＭＰａ）以上、さらに好ましくは５ｋｇ／ｃｍ２（４．９×１０－１ＭＰａ）以上である。０．５ｋｇ／ｃｍ２以上であると、接着フィルム２２Ａと被着体６との間に存在するボイドを容易に消滅させることができる。加圧雰囲気の圧力は、好ましくは２０ｋｇ／ｃｍ２（１．９６ＭＰａ）以下、より好ましくは１８ｋｇ／ｃｍ２（１．７７ＭＰａ）以下、さらに好ましくは１５ｋｇ／ｃｍ２（１．４７ＭＰａ）以下である。２０ｋｇ／ｃｍ２以下であると、過度な加圧による接着フィルム２２Ａのはみ出しを抑制できる。 Examples of the method of heating under pressure include a method of heating theadherend 61 with a semiconductor element arranged in a chamber filled with an inert gas.
The pressure of the pressurized atmosphere is preferably 0.5 kg / cm 2 (4.9 × 10 −2 MPa) or more, more preferably 1 kg / cm 2 (9.8 × 10 −2 MPa) or more, and further preferably 5 kg. / Cm 2 (4.9 × 10 −1 MPa) or more. If it is 0.5 kg / cm 2 or more, voids existing between theadhesive film 22A and the adherend 6 can be easily eliminated. The pressure of the pressurized atmosphere is preferably 20kg / cm 2 (1.96MPa), more preferably 18kg / cm 2 (1.77MPa) or less, more preferably not more than 15kg / cm 2 (1.47MPa). The protrusion of the adhesive film 22A due to excessive pressurization can be suppressed as it is 20 kg / cm 2 or less.
加圧雰囲気の圧力は、好ましくは０．５ｋｇ／ｃｍ２（４．９×１０－２ＭＰａ）以上、より好ましくは１ｋｇ／ｃｍ２（９．８×１０－２ＭＰａ）以上、さらに好ましくは５ｋｇ／ｃｍ２（４．９×１０－１ＭＰａ）以上である。０．５ｋｇ／ｃｍ２以上であると、接着フィルム２２Ａと被着体６との間に存在するボイドを容易に消滅させることができる。加圧雰囲気の圧力は、好ましくは２０ｋｇ／ｃｍ２（１．９６ＭＰａ）以下、より好ましくは１８ｋｇ／ｃｍ２（１．７７ＭＰａ）以下、さらに好ましくは１５ｋｇ／ｃｍ２（１．４７ＭＰａ）以下である。２０ｋｇ／ｃｍ２以下であると、過度な加圧による接着フィルム２２Ａのはみ出しを抑制できる。 Examples of the method of heating under pressure include a method of heating the
The pressure of the pressurized atmosphere is preferably 0.5 kg / cm 2 (4.9 × 10 −2 MPa) or more, more preferably 1 kg / cm 2 (9.8 × 10 −2 MPa) or more, and further preferably 5 kg. / Cm 2 (4.9 × 10 −1 MPa) or more. If it is 0.5 kg / cm 2 or more, voids existing between the
加圧下で加熱する際の加熱温度は、好ましくは８０℃以上、より好ましくは１００℃以上、さらに好ましくは１２０℃以上、特に好ましくは１７０℃以上である。８０℃以上であると、接着フィルム２２Ａを適度な硬さとすることが可能で、加圧キュアによりボイドを効果的に消失させることができる。加熱温度は、好ましくは２６０℃以下、より好ましくは２００℃以下、より好ましくは１８０℃以下である。２６０℃以下であると、接着フィルム２２Ａの分解を防ぐことができる。
The heating temperature at the time of heating under pressure is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, further preferably 120 ° C. or higher, and particularly preferably 170 ° C. or higher. When the temperature is 80 ° C. or higher, the adhesive film 22A can have an appropriate hardness, and voids can be effectively eliminated by pressure curing. The heating temperature is preferably 260 ° C. or lower, more preferably 200 ° C. or lower, more preferably 180 ° C. or lower. When the temperature is 260 ° C. or lower, the adhesive film 22A can be prevented from being decomposed.
加熱時間は、好ましくは０．１時間以上、より好ましくは０．２時間以上、さらに好ましくは０．５時間以上である。０．１時間以上であると、加圧の効果を充分に得ることができる。加熱時間は、好ましくは２４時間以下、より好ましくは３時間以下、さらに好ましくは１時間以下である。
The heating time is preferably 0.1 hour or longer, more preferably 0.2 hour or longer, and further preferably 0.5 hour or longer. When it is 0.1 hour or longer, the effect of pressurization can be sufficiently obtained. The heating time is preferably 24 hours or less, more preferably 3 hours or less, and even more preferably 1 hour or less.
図１２に示すように、被着体６の端子部（インナーリード）の先端と半導体素子５Ａ上の電極パッド（図示しない）とをボンディングワイヤー７で電気的に接続するワイヤーボンディング工程を行う。ボンディングワイヤー７としては、例えば金線、アルミニウム線又は銅線などが用いられる。ワイヤーボンディングを行う際の温度は、好ましくは８０℃以上、より好ましくは１２０℃以上であり、該温度は、好ましくは２５０℃以下、より好ましくは１７５℃以下である。また、その加熱時間は数秒～数分間（例えば、１秒～１分間）行われる。結線は、前記温度範囲内となる様に加熱された状態で、超音波による振動エネルギーと印加加圧による圧着エネルギーの併用により行われる。
As shown in FIG. 12, a wire bonding step of electrically connecting the tip of the terminal portion (inner lead) of the adherend 6 and an electrode pad (not shown) on the semiconductor element 5A with a bonding wire 7 is performed. As the bonding wire 7, for example, a gold wire, an aluminum wire or a copper wire is used. The temperature during wire bonding is preferably 80 ° C. or higher, more preferably 120 ° C. or higher, and the temperature is preferably 250 ° C. or lower, more preferably 175 ° C. or lower. The heating time is several seconds to several minutes (for example, 1 second to 1 minute). The connection is performed by a combination of vibration energy by ultrasonic waves and pressure energy by pressurization while being heated so as to be within the temperature range.
続いて、封止樹脂８により半導体素子５Ａを封止する封止工程を行う。本工程は、被着体６に搭載された半導体素子５Ａやボンディングワイヤー７を保護する為に行われる。本工程は、封止用の樹脂を金型で成型することにより行う。封止樹脂８としては、例えばエポキシ系の樹脂を使用する。樹脂封止の際の加熱温度は、好ましくは１６５℃以上、より好ましくは１７０℃以上であり、該加熱温度は、好ましくは１８５℃以下、より好ましくは１８０℃以下である。
Subsequently, a sealing step of sealing the semiconductor element 5A with the sealing resin 8 is performed. This step is performed to protect the semiconductor element 5 </ b> A and the bonding wire 7 mounted on the adherend 6. This step is performed by molding a sealing resin with a mold. As the sealing resin 8, for example, an epoxy resin is used. The heating temperature at the time of resin sealing is preferably 165 ° C. or higher, more preferably 170 ° C. or higher, and the heating temperature is preferably 185 ° C. or lower, more preferably 180 ° C. or lower.
必要に応じて、封止後に更に加熱をしてもよい（後硬化工程）。これにより、封止工程で硬化不足の封止樹脂８を完全に硬化できる。加熱温度は適宜設定できる。
If necessary, it may be further heated after sealing (post-curing step). Thereby, the sealing resin 8 which is insufficiently cured in the sealing process can be completely cured. The heating temperature can be set as appropriate.
（変形例１）
変形例１では、ダイシング・ダイボンドフィルム１０に半導体ウエハ４Ｐを圧着する。次いで、ダイシング・ダイボンドフィルム１０上に配置された半導体ウエハ４Ｐの内部に改質領域４１を形成して、分割ウエハ４を得る。 (Modification 1)
In the first modification, thesemiconductor wafer 4P is pressure-bonded to the dicing die-bonding film 10. Next, the modified region 41 is formed inside the semiconductor wafer 4 </ b> P disposed on the dicing die bond film 10 to obtain the divided wafer 4.
変形例１では、ダイシング・ダイボンドフィルム１０に半導体ウエハ４Ｐを圧着する。次いで、ダイシング・ダイボンドフィルム１０上に配置された半導体ウエハ４Ｐの内部に改質領域４１を形成して、分割ウエハ４を得る。 (Modification 1)
In the first modification, the
（変形例２）
変形例２では、接着フィルム２２Ａを熱硬化することなく、ワイヤーボンディング工程を行う。 (Modification 2)
InModification 2, the wire bonding step is performed without thermosetting the adhesive film 22A.
変形例２では、接着フィルム２２Ａを熱硬化することなく、ワイヤーボンディング工程を行う。 (Modification 2)
In
（変形例３）
周辺部１２ｂは、放射線照射により硬化された部分である。 (Modification 3)
Theperipheral part 12b is a part cured by radiation irradiation.
周辺部１２ｂは、放射線照射により硬化された部分である。 (Modification 3)
The
（変形例４）
中央部１２ａは、放射線照射により硬化されていない部分である。 (Modification 4)
The central portion 12a is a portion that is not cured by radiation irradiation.
中央部１２ａは、放射線照射により硬化されていない部分である。 (Modification 4)
The central portion 12a is a portion that is not cured by radiation irradiation.
以上のとおり、実施形態１の半導体装置の製造方法は、ダイシング・ダイボンドフィルム１０、及び接着剤層３上に配置された、改質領域４１を備える分割ウエハ４を備える分割体２１を準備する工程と、ダイシングシート１を拡張することにより、改質領域４１を起点に分割ウエハ４及び接着剤層３を分断する工程と、分割ウエハ４及び接着剤層３を分断する工程の後に、周辺部１２ｂを加熱する工程とを含む。実施形態１の半導体装置の製造方法は、分割ウエハ４及び接着剤層３を分断する工程により得られたダイボンド用チップ２Ａを被着体６に圧着する工程などをさらに含む。
As described above, the manufacturing method of the semiconductor device according to the first embodiment is a process of preparing the divided body 21 including the dicing die bond film 10 and the divided wafer 4 including the modified region 41 disposed on the adhesive layer 3. Then, by expanding the dicing sheet 1, after the step of dividing the divided wafer 4 and the adhesive layer 3 from the modified region 41 and the step of dividing the divided wafer 4 and the adhesive layer 3, the peripheral portion 12 b Heating. The manufacturing method of the semiconductor device of Embodiment 1 further includes a step of pressure bonding the die bonding chip 2A obtained by the step of dividing the divided wafer 4 and the adhesive layer 3 to the adherend 6 and the like.
分割体２１を準備する工程は、分割ウエハ４を形成するステップを含む。分割ウエハ４を形成するステップは、分割予定ライン４Ｌに沿ってレーザー光１００を照射することにより、半導体ウエハ４Ｐの内部に改質領域４１を形成する段階を含む。
The step of preparing the divided body 21 includes a step of forming the divided wafer 4. The step of forming the divided wafer 4 includes a step of forming the modified region 41 inside the semiconductor wafer 4P by irradiating the laser beam 100 along the planned division line 4L.
以下、本発明に関し実施例を用いて詳細に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.
［基材］
実施例及び比較例で使用した基材Ａ～Ｇを説明する。基材Ａ～Ｇの厚みを表１に示す。
基材Ａ：グンゼ社製のファンクレア ＮＲＢ＃１１５（エチレン酢酸ビニル共重合体フィルム）
基材Ｂ：グンゼ社製のファンクレア ＮＲＢ＃１３５（エチレン酢酸ビニル共重合体フィルム）
基材Ｃ：オージーフィルム社製のＰＥ－５（エチレン－アクリル酸エステル共重合体フィルム）
基材Ｄ：ロンシール工業社製のＨＬフィルム（ポリ塩化ビニルフィルム）
基材Ｅ：オージーフィルム社製のＰＰ－１（ポリプロピレンフィルム）
基材Ｆ：ポリプロピレン（８０％）ポリエチレン（２０％）２層フィルム
基材Ｇ：ポリプロピレン（８０％）ポリエチレン（２０％）２層フィルム [Base material]
The base materials A to G used in Examples and Comparative Examples will be described. Table 1 shows the thicknesses of the substrates A to G.
Base material A: Fanclaire NRB # 115 (ethylene vinyl acetate copolymer film) manufactured by Gunze
Base material B: Fanclaire NRB # 135 (ethylene vinyl acetate copolymer film) manufactured by Gunze
Base material C: PE-5 (ethylene-acrylic acid ester copolymer film) manufactured by Aussie Film
Base material D: HL film (polyvinyl chloride film) manufactured by Ron Seal Industry Co., Ltd.
Substrate E: PP-1 (polypropylene film) manufactured by Aussie Film
Base material F: Polypropylene (80%) polyethylene (20%) two-layer film Base material G: Polypropylene (80%) polyethylene (20%) two-layer film
実施例及び比較例で使用した基材Ａ～Ｇを説明する。基材Ａ～Ｇの厚みを表１に示す。
基材Ａ：グンゼ社製のファンクレア ＮＲＢ＃１１５（エチレン酢酸ビニル共重合体フィルム）
基材Ｂ：グンゼ社製のファンクレア ＮＲＢ＃１３５（エチレン酢酸ビニル共重合体フィルム）
基材Ｃ：オージーフィルム社製のＰＥ－５（エチレン－アクリル酸エステル共重合体フィルム）
基材Ｄ：ロンシール工業社製のＨＬフィルム（ポリ塩化ビニルフィルム）
基材Ｅ：オージーフィルム社製のＰＰ－１（ポリプロピレンフィルム）
基材Ｆ：ポリプロピレン（８０％）ポリエチレン（２０％）２層フィルム
基材Ｇ：ポリプロピレン（８０％）ポリエチレン（２０％）２層フィルム [Base material]
The base materials A to G used in Examples and Comparative Examples will be described. Table 1 shows the thicknesses of the substrates A to G.
Base material A: Fanclaire NRB # 115 (ethylene vinyl acetate copolymer film) manufactured by Gunze
Base material B: Fanclaire NRB # 135 (ethylene vinyl acetate copolymer film) manufactured by Gunze
Base material C: PE-5 (ethylene-acrylic acid ester copolymer film) manufactured by Aussie Film
Base material D: HL film (polyvinyl chloride film) manufactured by Ron Seal Industry Co., Ltd.
Substrate E: PP-1 (polypropylene film) manufactured by Aussie Film
Base material F: Polypropylene (80%) polyethylene (20%) two-layer film Base material G: Polypropylene (80%) polyethylene (20%) two-layer film
［ダイシング・ダイボンドフィルムの作製］
（実施例１）
冷却管、窒素導入管、温度計、及び、撹拌装置を備えた反応容器に、アクリル酸－２－エチルヘキシル（以下、「２ＥＨＡ」ともいう。）８６．４部、アクリル酸－２－ヒドロキシエチル（以下、「ＨＥＡ」ともいう。）１３．６部、過酸化ベンゾイル０．２部、及び、トルエン６５部を入れ、窒素気流中で６１℃にて６時間重合処理をし、アクリル系ポリマーＢを得た。アクリル系ポリマーＢに２－メタクリロイルオキシエチルイソシアネート（以下、「ＭＯＩ」ともいう。）１４．６部を加え、空気気流中で５０℃にて４８時間、付加反応処理をし、アクリル系ポリマーＢ’を得た。アクリル系ポリマーＢ’１００部に対し、ポリイソシアネート化合物（商品名「コロネートＬ」、日本ポリウレタン（株）製）２部、及び、光重合開始剤（商品名「イルガキュア６５１」、チバ・スペシャルティ・ケミカルズ社製）５部を加えて、粘着剤組成物溶液を得た。粘着剤組成物溶液を、離型処理フィルム上に塗布し、１２０℃で２分間加熱乾燥し、厚さ３０μｍの粘着剤層を形成した。次いで、粘着剤層に、基材Ａを貼り合せた。その後、マスクを介して、粘着剤層のうち１２ｉｎｃｈサイズのウェハが貼り付けられる予定の部分に紫外線を４００ｍＪ／ｃｍ２照射し、紫外線硬化した。得られたダイシングシートは、基材Ａ、基材Ａ上に配置された粘着剤層を有する。 [Production of dicing die bond film]
(Example 1)
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, 86.4 parts of 2-ethylhexyl acrylate (hereinafter also referred to as “2EHA”), 2-hydroxyethyl acrylate ( Hereinafter, it is also referred to as “HEA”.) 13.6 parts, 0.2 part of benzoyl peroxide, and 65 parts of toluene are put into a nitrogen gas stream and polymerized at 61 ° C. for 6 hours to obtain acrylic polymer B. Obtained. To acrylic polymer B, 14.6 parts of 2-methacryloyloxyethyl isocyanate (hereinafter also referred to as “MOI”) was added, and an addition reaction treatment was carried out in an air stream at 50 ° C. for 48 hours to obtain acrylic polymer B ′. Got. For 100 parts of acrylic polymer B ′, 2 parts of polyisocyanate compound (trade name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.) and photopolymerization initiator (trade name “Irgacure 651”, Ciba Specialty Chemicals) 5 parts) was added to obtain an adhesive composition solution. The pressure-sensitive adhesive composition solution was applied on a release treatment film and dried by heating at 120 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 30 μm. Subsequently, the base material A was bonded to the pressure-sensitive adhesive layer. Thereafter, ultraviolet light was irradiated at 400 mJ / cm 2 on the portion of the pressure-sensitive adhesive layer where a 12 inch wafer was to be attached, and cured by ultraviolet light. The obtained dicing sheet has the adhesive layer arrange | positioned on the base material A and the base material A. FIG.
（実施例１）
冷却管、窒素導入管、温度計、及び、撹拌装置を備えた反応容器に、アクリル酸－２－エチルヘキシル（以下、「２ＥＨＡ」ともいう。）８６．４部、アクリル酸－２－ヒドロキシエチル（以下、「ＨＥＡ」ともいう。）１３．６部、過酸化ベンゾイル０．２部、及び、トルエン６５部を入れ、窒素気流中で６１℃にて６時間重合処理をし、アクリル系ポリマーＢを得た。アクリル系ポリマーＢに２－メタクリロイルオキシエチルイソシアネート（以下、「ＭＯＩ」ともいう。）１４．６部を加え、空気気流中で５０℃にて４８時間、付加反応処理をし、アクリル系ポリマーＢ’を得た。アクリル系ポリマーＢ’１００部に対し、ポリイソシアネート化合物（商品名「コロネートＬ」、日本ポリウレタン（株）製）２部、及び、光重合開始剤（商品名「イルガキュア６５１」、チバ・スペシャルティ・ケミカルズ社製）５部を加えて、粘着剤組成物溶液を得た。粘着剤組成物溶液を、離型処理フィルム上に塗布し、１２０℃で２分間加熱乾燥し、厚さ３０μｍの粘着剤層を形成した。次いで、粘着剤層に、基材Ａを貼り合せた。その後、マスクを介して、粘着剤層のうち１２ｉｎｃｈサイズのウェハが貼り付けられる予定の部分に紫外線を４００ｍＪ／ｃｍ２照射し、紫外線硬化した。得られたダイシングシートは、基材Ａ、基材Ａ上に配置された粘着剤層を有する。 [Production of dicing die bond film]
(Example 1)
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, 86.4 parts of 2-ethylhexyl acrylate (hereinafter also referred to as “2EHA”), 2-hydroxyethyl acrylate ( Hereinafter, it is also referred to as “HEA”.) 13.6 parts, 0.2 part of benzoyl peroxide, and 65 parts of toluene are put into a nitrogen gas stream and polymerized at 61 ° C. for 6 hours to obtain acrylic polymer B. Obtained. To acrylic polymer B, 14.6 parts of 2-methacryloyloxyethyl isocyanate (hereinafter also referred to as “MOI”) was added, and an addition reaction treatment was carried out in an air stream at 50 ° C. for 48 hours to obtain acrylic polymer B ′. Got. For 100 parts of acrylic polymer B ′, 2 parts of polyisocyanate compound (trade name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.) and photopolymerization initiator (trade name “Irgacure 651”, Ciba Specialty Chemicals) 5 parts) was added to obtain an adhesive composition solution. The pressure-sensitive adhesive composition solution was applied on a release treatment film and dried by heating at 120 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 30 μm. Subsequently, the base material A was bonded to the pressure-sensitive adhesive layer. Thereafter, ultraviolet light was irradiated at 400 mJ / cm 2 on the portion of the pressure-sensitive adhesive layer where a 12 inch wafer was to be attached, and cured by ultraviolet light. The obtained dicing sheet has the adhesive layer arrange | positioned on the base material A and the base material A. FIG.
表２に示した割合でアクリル樹脂、エポキシ樹脂Ａ、エポキシ樹脂Ｂ、フェノール樹脂、シリカ、及び触媒をメチルエチルケトンに溶解して濃度４０～５０重量％の接着剤組成物溶液を調製した。
Acrylic resin, epoxy resin A, epoxy resin B, phenol resin, silica, and catalyst were dissolved in methyl ethyl ketone at a ratio shown in Table 2 to prepare an adhesive composition solution having a concentration of 40 to 50% by weight.
各成分の詳細は以下のとおりである。
アクリル樹脂：ナガセケムテックス社製 ＳＧ－７０８－６（Ｔｇ：４℃）
エポキシ樹脂Ａ：東都化成株式会社製 ＫＩ－３０００（固形）
エポキシ樹脂Ｂ：三菱化学株式会社製 ＪＥＲ ＹＬ９８０（液状）
フェノール樹脂：明和化成株式会社製 ＭＥＨ－７８００Ｈ（固形）
シリカ：アドマテックス株式会社製 ＳＥ－２０５０ＭＣ（平均粒径：０．５μｍ）
触媒：北興化学株式会社製 ＴＰＰ－Ｋ Details of each component are as follows.
Acrylic resin: SG-708-6 (Tg: 4 ° C) manufactured by Nagase ChemteX Corporation
Epoxy resin A: KI-3000 (solid) manufactured by Toto Kasei Co., Ltd.
Epoxy resin B: JER YL980 (liquid) manufactured by Mitsubishi Chemical Corporation
Phenolic resin: MEH-7800H (solid) manufactured by Meiwa Kasei Co., Ltd.
Silica: SE-2050MC manufactured by Admatechs Co., Ltd. (average particle size: 0.5 μm)
Catalyst: TPP-K manufactured by Hokuko Chemical Co., Ltd.
アクリル樹脂：ナガセケムテックス社製 ＳＧ－７０８－６（Ｔｇ：４℃）
エポキシ樹脂Ａ：東都化成株式会社製 ＫＩ－３０００（固形）
エポキシ樹脂Ｂ：三菱化学株式会社製 ＪＥＲ ＹＬ９８０（液状）
フェノール樹脂：明和化成株式会社製 ＭＥＨ－７８００Ｈ（固形）
シリカ：アドマテックス株式会社製 ＳＥ－２０５０ＭＣ（平均粒径：０．５μｍ）
触媒：北興化学株式会社製 ＴＰＰ－Ｋ Details of each component are as follows.
Acrylic resin: SG-708-6 (Tg: 4 ° C) manufactured by Nagase ChemteX Corporation
Epoxy resin A: KI-3000 (solid) manufactured by Toto Kasei Co., Ltd.
Epoxy resin B: JER YL980 (liquid) manufactured by Mitsubishi Chemical Corporation
Phenolic resin: MEH-7800H (solid) manufactured by Meiwa Kasei Co., Ltd.
Silica: SE-2050MC manufactured by Admatechs Co., Ltd. (average particle size: 0.5 μm)
Catalyst: TPP-K manufactured by Hokuko Chemical Co., Ltd.
調製した接着剤組成物溶液を、シリコーン離型処理した厚み５０μｍのポリエチレンテレフタレートフィルムに塗布した後、１３０℃で２分間乾燥させることにより、厚み３０μｍの接着剤塗膜を作製した。接着剤塗膜から、直径３３０ｍｍの円形状の接着剤層を切り出した。
The prepared adhesive composition solution was applied to a 50 μm-thick polyethylene terephthalate film subjected to silicone release treatment, and then dried at 130 ° C. for 2 minutes to prepare an adhesive coating film having a thickness of 30 μm. A circular adhesive layer having a diameter of 330 mm was cut out from the adhesive coating film.
粘着剤層に、円形状の接着剤層を貼り合わせて、ダイシング・ダイボンドフィルムを作製した。
A circular adhesive layer was bonded to the pressure-sensitive adhesive layer to prepare a dicing die-bonding film.
（実施例２）
基材Ａに代えて基材Ｂを使用したこと以外は実施例１と同様の方法でダイシング・ダイボンドフィルムを作製した。 (Example 2)
A dicing die-bonding film was produced in the same manner as in Example 1 except that the base material B was used instead of the base material A.
基材Ａに代えて基材Ｂを使用したこと以外は実施例１と同様の方法でダイシング・ダイボンドフィルムを作製した。 (Example 2)
A dicing die-bonding film was produced in the same manner as in Example 1 except that the base material B was used instead of the base material A.
（実施例３）
基材Ａに代えて基材Ｃを使用したこと以外は実施例１と同様の方法でダイシング・ダイボンドフィルムを作製した。 (Example 3)
A dicing die-bonding film was produced in the same manner as in Example 1 except that the substrate C was used instead of the substrate A.
基材Ａに代えて基材Ｃを使用したこと以外は実施例１と同様の方法でダイシング・ダイボンドフィルムを作製した。 (Example 3)
A dicing die-bonding film was produced in the same manner as in Example 1 except that the substrate C was used instead of the substrate A.
（実施例４）
基材Ａに代えて基材Ｄを使用したこと以外は実施例１と同様の方法でダイシング・ダイボンドフィルムを作製した。 Example 4
A dicing die-bonding film was produced in the same manner as in Example 1 except that the substrate D was used instead of the substrate A.
基材Ａに代えて基材Ｄを使用したこと以外は実施例１と同様の方法でダイシング・ダイボンドフィルムを作製した。 Example 4
A dicing die-bonding film was produced in the same manner as in Example 1 except that the substrate D was used instead of the substrate A.
（比較例１）
基材Ａに代えて基材Ｅを使用したこと以外は実施例１と同様の方法でダイシング・ダイボンドフィルムを作製した。 (Comparative Example 1)
A dicing die-bonding film was produced in the same manner as in Example 1 except that the substrate E was used instead of the substrate A.
基材Ａに代えて基材Ｅを使用したこと以外は実施例１と同様の方法でダイシング・ダイボンドフィルムを作製した。 (Comparative Example 1)
A dicing die-bonding film was produced in the same manner as in Example 1 except that the substrate E was used instead of the substrate A.
（比較例２）
基材Ａに代えて基材Ｆを使用したこと以外は実施例１と同様の方法でダイシング・ダイボンドフィルムを作製した。 (Comparative Example 2)
A dicing die-bonding film was produced in the same manner as in Example 1 except that the base material F was used instead of the base material A.
基材Ａに代えて基材Ｆを使用したこと以外は実施例１と同様の方法でダイシング・ダイボンドフィルムを作製した。 (Comparative Example 2)
A dicing die-bonding film was produced in the same manner as in Example 1 except that the base material F was used instead of the base material A.
（比較例３）
基材Ａに代えて基材Ｇを使用したこと以外は実施例１と同様の方法でダイシング・ダイボンドフィルムを作製した。 (Comparative Example 3)
A dicing die-bonding film was produced in the same manner as in Example 1 except that the base material G was used instead of the base material A.
基材Ａに代えて基材Ｇを使用したこと以外は実施例１と同様の方法でダイシング・ダイボンドフィルムを作製した。 (Comparative Example 3)
A dicing die-bonding film was produced in the same manner as in Example 1 except that the base material G was used instead of the base material A.
［評価１］
ダイシングシートについて以下の評価を行った。結果を表１に示す。 [Evaluation 1]
The following evaluation was performed on the dicing sheet. The results are shown in Table 1.
ダイシングシートについて以下の評価を行った。結果を表１に示す。 [Evaluation 1]
The following evaluation was performed on the dicing sheet. The results are shown in Table 1.
（加熱収縮率）
ダイシング・ダイボンドフィルムから接着剤層を剥がすことにより、ダイシングシートを得た。ダイシングシートから、ＭＤ方向の長さ１５０ｍｍ、幅２５ｍｍの短冊状の試験片５００を切り出した。図１６に示すように、試験片５００に１００ｍｍの間隔で２つの標線５０１ａ、５０１ｂを入れた。竿５０２に試験片５００を吊り下げ、試験片５００を乾燥機で１００℃で１分加熱した。冷却後に、２つの標線５０１ａ、５０１ｂの間隔を測定し、下記式にて加熱収縮率を求めた。
加熱収縮率＝加熱後の標線間距離／加熱前の標線間距離×１００ (Heat shrinkage)
A dicing sheet was obtained by removing the adhesive layer from the dicing die-bonding film. A strip-shapedtest piece 500 having a length of 150 mm in the MD direction and a width of 25 mm was cut out from the dicing sheet. As shown in FIG. 16, two marked lines 501a and 501b were put in the test piece 500 at an interval of 100 mm. The test piece 500 was suspended from the basket 502, and the test piece 500 was heated at 100 ° C. for 1 minute with a dryer. After cooling, the distance between the two marked lines 501a and 501b was measured, and the heat shrinkage rate was determined by the following formula.
Heat shrinkage rate = distance between marked lines after heating / distance between marked lines before heating × 100
ダイシング・ダイボンドフィルムから接着剤層を剥がすことにより、ダイシングシートを得た。ダイシングシートから、ＭＤ方向の長さ１５０ｍｍ、幅２５ｍｍの短冊状の試験片５００を切り出した。図１６に示すように、試験片５００に１００ｍｍの間隔で２つの標線５０１ａ、５０１ｂを入れた。竿５０２に試験片５００を吊り下げ、試験片５００を乾燥機で１００℃で１分加熱した。冷却後に、２つの標線５０１ａ、５０１ｂの間隔を測定し、下記式にて加熱収縮率を求めた。
加熱収縮率＝加熱後の標線間距離／加熱前の標線間距離×１００ (Heat shrinkage)
A dicing sheet was obtained by removing the adhesive layer from the dicing die-bonding film. A strip-shaped
Heat shrinkage rate = distance between marked lines after heating / distance between marked lines before heating × 100
（３％引張応力）
ダイシング・ダイボンドフィルムから接着剤層を剥がすことにより、ダイシングシートを得た。ダイシングシートから、ＭＤ方向の長さ１５０ｍｍ、幅２５ｍの短冊状の測定片を切り出した。引っ張り試験機（オートグラフ、島津製作所社製）を用いて、２３℃、引張速度３００ｍｍ／分、チャック間距離１００ｍｍの条件下で引張試験を行い、試験片が３％伸びた時点の引張応力を読み取った。 (3% tensile stress)
A dicing sheet was obtained by removing the adhesive layer from the dicing die-bonding film. A strip-shaped measurement piece having a length of 150 mm in the MD direction and a width of 25 m was cut out from the dicing sheet. Using a tensile tester (Autograph, manufactured by Shimadzu Corporation), a tensile test was performed under the conditions of 23 ° C., a tensile speed of 300 mm / min, and a distance between chucks of 100 mm. I read it.
ダイシング・ダイボンドフィルムから接着剤層を剥がすことにより、ダイシングシートを得た。ダイシングシートから、ＭＤ方向の長さ１５０ｍｍ、幅２５ｍの短冊状の測定片を切り出した。引っ張り試験機（オートグラフ、島津製作所社製）を用いて、２３℃、引張速度３００ｍｍ／分、チャック間距離１００ｍｍの条件下で引張試験を行い、試験片が３％伸びた時点の引張応力を読み取った。 (3% tensile stress)
A dicing sheet was obtained by removing the adhesive layer from the dicing die-bonding film. A strip-shaped measurement piece having a length of 150 mm in the MD direction and a width of 25 m was cut out from the dicing sheet. Using a tensile tester (Autograph, manufactured by Shimadzu Corporation), a tensile test was performed under the conditions of 23 ° C., a tensile speed of 300 mm / min, and a distance between chucks of 100 mm. I read it.
（６％引張応力）
ダイシング・ダイボンドフィルムから接着剤層を剥がすことにより、ダイシングシートを得た。ダイシングシートから、ＭＤ方向の長さ１５０ｍｍ、幅２５ｍの短冊状の測定片を切り出した。引っ張り試験機（オートグラフ、島津製作所社製）を用いて、２３℃、引張速度３００ｍｍ／分、チャック間距離１００ｍｍの条件下で引張試験を行い、試験片が６％伸びた時点の引張応力を読み取った。 (6% tensile stress)
A dicing sheet was obtained by removing the adhesive layer from the dicing die-bonding film. A strip-shaped measurement piece having a length of 150 mm in the MD direction and a width of 25 m was cut out from the dicing sheet. Using a tensile tester (Autograph, manufactured by Shimadzu Corporation), a tensile test was performed under the conditions of 23 ° C., a tensile speed of 300 mm / min, and a distance between chucks of 100 mm. I read it.
ダイシング・ダイボンドフィルムから接着剤層を剥がすことにより、ダイシングシートを得た。ダイシングシートから、ＭＤ方向の長さ１５０ｍｍ、幅２５ｍの短冊状の測定片を切り出した。引っ張り試験機（オートグラフ、島津製作所社製）を用いて、２３℃、引張速度３００ｍｍ／分、チャック間距離１００ｍｍの条件下で引張試験を行い、試験片が６％伸びた時点の引張応力を読み取った。 (6% tensile stress)
A dicing sheet was obtained by removing the adhesive layer from the dicing die-bonding film. A strip-shaped measurement piece having a length of 150 mm in the MD direction and a width of 25 m was cut out from the dicing sheet. Using a tensile tester (Autograph, manufactured by Shimadzu Corporation), a tensile test was performed under the conditions of 23 ° C., a tensile speed of 300 mm / min, and a distance between chucks of 100 mm. I read it.
［評価２］
ダイシング・ダイボンドフィルムを用いて以下の評価を行った。結果を表１に示す。 [Evaluation 2]
The following evaluation was performed using a dicing die-bonding film. The results are shown in Table 1.
ダイシング・ダイボンドフィルムを用いて以下の評価を行った。結果を表１に示す。 [Evaluation 2]
The following evaluation was performed using a dicing die-bonding film. The results are shown in Table 1.
（初期のピックアップ成功率）
レーザー加工装置として株式会社東京精密製、ＭＬ３００－Ｉｎｔｅｇｒａｔｉｏｎを用いて、１２ｉｎｃｈサイズの半導体ウェハの内部に集光点を合わせ、格子状（１０ｍｍ×１０ｍｍ）の分割予定ラインに沿って半導体ウェハの表面（おもてめん）または裏面側からレーザー光を照射し、半導体ウェハの内部に改質領域を形成した。その後、半導体ウェハ表面にバックグラインド用保護テープを貼り合せ、ディスコ社製バックグラインダーＤＧＰ８７６０を用いて半導体ウェハの厚みが３０μｍになるように裏面を研削した。レーザー光照射条件を以下に示す。
（Ａ）レーザー光
レーザー光源 半導体レーザー励起Ｎｄ：ＹＡＧレーザー
波長 １０６４ｎｍ
レーザー光スポット断面積 ３．１４×１０－８ｃｍ２
発振形態 Ｑスイッチパルス
繰り返し周波数 １００ｋＨｚ
パルス幅 ３０ｎｓ
出力 ２０μＪ／パルス
レーザー光品質 ＴＥＭ００ ４０
偏光特性 直線偏光
（Ｂ）集光用レンズ
倍率 ５０倍
ＮＡ ０．５５
レーザー光波長に対する透過率 ６０％
（Ｃ）半導体基板が載置される裁置台の移動速度 １００ｍｍ／秒
ダイシング・ダイボンドフィルムに、レーザー光による前処理を行った半導体ウェハ及びダイシングリングを貼り合わせた後、ディスコ社製ダイセパレーターＤＤＳ２３００を用いて半導体ウェハの割断及びダイシングシートの熱収縮を行うことにより、サンプルを得た。すなわち、まずクールエキスパンダーユニットで、エキスパンド温度－１５℃、エキスパンド速度２００ｍｍ／秒、エキスパンド量１２ｍｍの条件で半導体ウェハを割断した。
その後、ヒートエキスパンダーユニットで、エキスパンド量１０ｍｍ、ヒート温度２５０℃、風量４０Ｌ／ｍｉｎ、ヒート距離２０ｍｍ、ローテーションスピード３°／ｓｅｃの条件でダイシングシートを熱収縮させることにより、サンプルを得た。サンプルについて株式会社新川社製ダイボンダーＳＰＡ－３００を用いてピックアップ評価を行った。すなわち、エキスパンド量３ｍｍ、ニードル本数９本、ニードル突き上げ量４００μｍ、突き上げ速度１０ｍｍ／ｓｅｃ、突き上げ時間１ｓｅｃの条件で、半導体チップ及び半導体チップと接する接着剤層を有するダイボンド用チップを突き上げる動作を１００回行うことにより、ピックアップ成功回数を評価した。 (Initial pickup success rate)
Using ML300-Integration, manufactured by Tokyo Seimitsu Co., Ltd. as the laser processing device, the focusing point is aligned with the interior of a 12 inch semiconductor wafer, and the surface of the semiconductor wafer (10 mm × 10 mm) along the planned dividing line (10 mm × 10 mm) Otemen) or laser light was irradiated from the back side to form a modified region inside the semiconductor wafer. Thereafter, a protective tape for back grinding was bonded to the surface of the semiconductor wafer, and the back surface was ground using a disco back grinder DGP8760 so that the thickness of the semiconductor wafer was 30 μm. The laser light irradiation conditions are shown below.
(A) Laser light Laser light source Semiconductor laser excitation Nd: YAG laser Wavelength 1064 nm
Laser light spot cross section 3.14 × 10 −8 cm 2
Oscillation form Q switch pulse Repetition frequency 100kHz
Pulse width 30ns
Output 20μJ / pulse Laser light quality TEM00 40
Polarization characteristics Linearly polarized light (B)Condensing lens Magnification 50 times NA 0.55
60% transmittance for laser wavelength
(C) The moving speed of the mounting table on which the semiconductor substrate is placed 100 mm / sec. After the semiconductor wafer and the dicing ring that have been pre-processed with laser light are bonded to the dicing die-bonding film, the die separator DDS2300 manufactured by DISCO Corporation is used. A sample was obtained by cleaving the semiconductor wafer and heat shrinking the dicing sheet. That is, first, the semiconductor wafer was cleaved by a cool expander unit under the conditions of an expansion temperature of −15 ° C., an expansion speed of 200 mm / second, and an expansion amount of 12 mm.
Then, the sample was obtained by heat-shrinking the dicing sheet with a heat expander unit under the conditions of an expansion amount of 10 mm, a heat temperature of 250 ° C., an air volume of 40 L / min, a heat distance of 20 mm, and a rotation speed of 3 ° / sec. The sample was evaluated for pickup using a die bonder SPA-300 manufactured by Shinkawa Co., Ltd. That is, the operation of pushing up a die bonding chip having a semiconductor chip and an adhesive layer in contact with thesemiconductor chip 100 times under the conditions of an expansion amount of 3 mm, a needle number of 9, a needle push-up amount of 400 μm, a push-up speed of 10 mm / sec, and a push-up time of 1 sec. By doing so, the number of successful pick-ups was evaluated.
レーザー加工装置として株式会社東京精密製、ＭＬ３００－Ｉｎｔｅｇｒａｔｉｏｎを用いて、１２ｉｎｃｈサイズの半導体ウェハの内部に集光点を合わせ、格子状（１０ｍｍ×１０ｍｍ）の分割予定ラインに沿って半導体ウェハの表面（おもてめん）または裏面側からレーザー光を照射し、半導体ウェハの内部に改質領域を形成した。その後、半導体ウェハ表面にバックグラインド用保護テープを貼り合せ、ディスコ社製バックグラインダーＤＧＰ８７６０を用いて半導体ウェハの厚みが３０μｍになるように裏面を研削した。レーザー光照射条件を以下に示す。
（Ａ）レーザー光
レーザー光源 半導体レーザー励起Ｎｄ：ＹＡＧレーザー
波長 １０６４ｎｍ
レーザー光スポット断面積 ３．１４×１０－８ｃｍ２
発振形態 Ｑスイッチパルス
繰り返し周波数 １００ｋＨｚ
パルス幅 ３０ｎｓ
出力 ２０μＪ／パルス
レーザー光品質 ＴＥＭ００ ４０
偏光特性 直線偏光
（Ｂ）集光用レンズ
倍率 ５０倍
ＮＡ ０．５５
レーザー光波長に対する透過率 ６０％
（Ｃ）半導体基板が載置される裁置台の移動速度 １００ｍｍ／秒
ダイシング・ダイボンドフィルムに、レーザー光による前処理を行った半導体ウェハ及びダイシングリングを貼り合わせた後、ディスコ社製ダイセパレーターＤＤＳ２３００を用いて半導体ウェハの割断及びダイシングシートの熱収縮を行うことにより、サンプルを得た。すなわち、まずクールエキスパンダーユニットで、エキスパンド温度－１５℃、エキスパンド速度２００ｍｍ／秒、エキスパンド量１２ｍｍの条件で半導体ウェハを割断した。
その後、ヒートエキスパンダーユニットで、エキスパンド量１０ｍｍ、ヒート温度２５０℃、風量４０Ｌ／ｍｉｎ、ヒート距離２０ｍｍ、ローテーションスピード３°／ｓｅｃの条件でダイシングシートを熱収縮させることにより、サンプルを得た。サンプルについて株式会社新川社製ダイボンダーＳＰＡ－３００を用いてピックアップ評価を行った。すなわち、エキスパンド量３ｍｍ、ニードル本数９本、ニードル突き上げ量４００μｍ、突き上げ速度１０ｍｍ／ｓｅｃ、突き上げ時間１ｓｅｃの条件で、半導体チップ及び半導体チップと接する接着剤層を有するダイボンド用チップを突き上げる動作を１００回行うことにより、ピックアップ成功回数を評価した。 (Initial pickup success rate)
Using ML300-Integration, manufactured by Tokyo Seimitsu Co., Ltd. as the laser processing device, the focusing point is aligned with the interior of a 12 inch semiconductor wafer, and the surface of the semiconductor wafer (10 mm × 10 mm) along the planned dividing line (10 mm × 10 mm) Otemen) or laser light was irradiated from the back side to form a modified region inside the semiconductor wafer. Thereafter, a protective tape for back grinding was bonded to the surface of the semiconductor wafer, and the back surface was ground using a disco back grinder DGP8760 so that the thickness of the semiconductor wafer was 30 μm. The laser light irradiation conditions are shown below.
(A) Laser light Laser light source Semiconductor laser excitation Nd: YAG laser Wavelength 1064 nm
Laser light spot cross section 3.14 × 10 −8 cm 2
Oscillation form Q switch pulse Repetition frequency 100kHz
Pulse width 30ns
Output 20μJ / pulse Laser light quality TEM00 40
Polarization characteristics Linearly polarized light (B)
60% transmittance for laser wavelength
(C) The moving speed of the mounting table on which the semiconductor substrate is placed 100 mm / sec. After the semiconductor wafer and the dicing ring that have been pre-processed with laser light are bonded to the dicing die-bonding film, the die separator DDS2300 manufactured by DISCO Corporation is used. A sample was obtained by cleaving the semiconductor wafer and heat shrinking the dicing sheet. That is, first, the semiconductor wafer was cleaved by a cool expander unit under the conditions of an expansion temperature of −15 ° C., an expansion speed of 200 mm / second, and an expansion amount of 12 mm.
Then, the sample was obtained by heat-shrinking the dicing sheet with a heat expander unit under the conditions of an expansion amount of 10 mm, a heat temperature of 250 ° C., an air volume of 40 L / min, a heat distance of 20 mm, and a rotation speed of 3 ° / sec. The sample was evaluated for pickup using a die bonder SPA-300 manufactured by Shinkawa Co., Ltd. That is, the operation of pushing up a die bonding chip having a semiconductor chip and an adhesive layer in contact with the
（一週間後のピックアップ成功率）
サンプルを２３℃で１週間保存し、その後同様の方法でピックアップ成功回数を評価した。 (Pickup success rate after one week)
Samples were stored at 23 ° C. for 1 week, and then the number of successful pickups was evaluated in the same manner.
サンプルを２３℃で１週間保存し、その後同様の方法でピックアップ成功回数を評価した。 (Pickup success rate after one week)
Samples were stored at 23 ° C. for 1 week, and then the number of successful pickups was evaluated in the same manner.
［評価３］
接着剤層について以下の評価を行った。結果を表２に示す。 [Evaluation 3]
The following evaluation was performed on the adhesive layer. The results are shown in Table 2.
接着剤層について以下の評価を行った。結果を表２に示す。 [Evaluation 3]
The following evaluation was performed on the adhesive layer. The results are shown in Table 2.
（ガラス転移温度）
接着剤層を６０℃の条件下で厚さ３００μｍになるまで重ねあわせ、次いで長さ３０ｍｍ、幅１０ｍｍの短冊状の測定片を切り出した。次に、動的粘弾性測定装置（ＲＳＡ（ＩＩ）、レオメトリックサイエンティフィック社製）を用いて、－３０℃～１００℃での貯蔵弾性率及び損失弾性率をチャック間距離２２．５ｍｍ、周波数１Ｈｚ、昇温速度１０℃／分の条件下にて測定し、ｔａｎδのピーク値によりガラス転移温度を得た。 (Glass-transition temperature)
The adhesive layer was laminated to a thickness of 300 μm under the condition of 60 ° C., and then a strip-shaped measurement piece having a length of 30 mm and a width of 10 mm was cut out. Next, using a dynamic viscoelasticity measuring device (RSA (II), manufactured by Rheometric Scientific), the storage elastic modulus and the loss elastic modulus at −30 ° C. to 100 ° C. were measured as the distance between chucks of 22.5 mm, Measurement was performed under conditions of a frequency of 1 Hz and a heating rate of 10 ° C./min, and a glass transition temperature was obtained from the peak value of tan δ.
接着剤層を６０℃の条件下で厚さ３００μｍになるまで重ねあわせ、次いで長さ３０ｍｍ、幅１０ｍｍの短冊状の測定片を切り出した。次に、動的粘弾性測定装置（ＲＳＡ（ＩＩ）、レオメトリックサイエンティフィック社製）を用いて、－３０℃～１００℃での貯蔵弾性率及び損失弾性率をチャック間距離２２．５ｍｍ、周波数１Ｈｚ、昇温速度１０℃／分の条件下にて測定し、ｔａｎδのピーク値によりガラス転移温度を得た。 (Glass-transition temperature)
The adhesive layer was laminated to a thickness of 300 μm under the condition of 60 ° C., and then a strip-shaped measurement piece having a length of 30 mm and a width of 10 mm was cut out. Next, using a dynamic viscoelasticity measuring device (RSA (II), manufactured by Rheometric Scientific), the storage elastic modulus and the loss elastic modulus at −30 ° C. to 100 ° C. were measured as the distance between chucks of 22.5 mm, Measurement was performed under conditions of a frequency of 1 Hz and a heating rate of 10 ° C./min, and a glass transition temperature was obtained from the peak value of tan δ.
１０ ダイシング・ダイボンドフィルム
１ ダイシングシート
２Ａ、２Ｂ、２Ｃ、２Ｄ、２Ｅ、２Ｆ、２Ｇ、２Ｈ ダイボンド用チップ
３ 接着剤層
４Ｐ 半導体ウエハ
４Ｌ 分割予定ライン
４ 分割ウエハ
５Ａ、５Ｂ、５Ｃ、５Ｄ、５Ｅ、５Ｆ、５Ｇ、５Ｈ 半導体素子
６ 被着体
７ ボンディングワイヤー
８ 封止樹脂
１１ 基材
１２ 粘着剤層
１２ａ 中央部
１２ｂ 周辺部
２１ 積層体
２２Ａ、２２Ｂ、２２Ｃ、２２Ｄ、２２Ｅ、２２Ｆ、２２Ｇ、２２Ｈ 接着フィルム
３１ ダイシングリング
３２ 吸着テーブル
３３ 突き上げ部
４１ 改質領域
５１ 分割構造体
６１ 半導体素子付き被着体
１００ レーザー光 10 Dicing diebond film 1 Dicing sheet 2A, 2B, 2C, 2D, 2E, 2F, 2G, 2H Die bonding chip 3 Adhesive layer 4P Semiconductor wafer 4L Divided line 4 Divided wafers 5A, 5B, 5C, 5D, 5E, 5F, 5G, 5H Semiconductor element 6 Substrate 7 Bonding wire 8 Sealing resin 11 Base material 12 Adhesive layer 12a Central part 12b Peripheral part 21 Laminated bodies 22A, 22B, 22C, 22D, 22E, 22F, 22G, 22H Adhesion Film 31 Dicing ring 32 Suction table 33 Push-up portion 41 Modified region 51 Divided structure 61 Substrate with semiconductor element 100 Laser beam
１ ダイシングシート
２Ａ、２Ｂ、２Ｃ、２Ｄ、２Ｅ、２Ｆ、２Ｇ、２Ｈ ダイボンド用チップ
３ 接着剤層
４Ｐ 半導体ウエハ
４Ｌ 分割予定ライン
４ 分割ウエハ
５Ａ、５Ｂ、５Ｃ、５Ｄ、５Ｅ、５Ｆ、５Ｇ、５Ｈ 半導体素子
６ 被着体
７ ボンディングワイヤー
８ 封止樹脂
１１ 基材
１２ 粘着剤層
１２ａ 中央部
１２ｂ 周辺部
２１ 積層体
２２Ａ、２２Ｂ、２２Ｃ、２２Ｄ、２２Ｅ、２２Ｆ、２２Ｇ、２２Ｈ 接着フィルム
３１ ダイシングリング
３２ 吸着テーブル
３３ 突き上げ部
４１ 改質領域
５１ 分割構造体
６１ 半導体素子付き被着体
１００ レーザー光 10 Dicing die
９１０ ダイシング・ダイボンドフィルム
９０１ ダイシングシート
９０３ 接着剤層
９０４ ウエハ
９０５Ａ、９０５Ｂ、９０５Ｃ、９０５Ｄ、９０５Ｅ、９０５Ｆ、９０５Ｇ、９０５Ｈ 半導体素子
９１１ 基材
９１２ 粘着剤層
９１２ｂ 周辺部 910 Dicing diebond film 901 Dicing sheet 903 Adhesive layer 904 Wafer 905A, 905B, 905C, 905D, 905E, 905F, 905G, 905H Semiconductor element 911 Base material 912 Adhesive layer 912b Peripheral part
９０１ ダイシングシート
９０３ 接着剤層
９０４ ウエハ
９０５Ａ、９０５Ｂ、９０５Ｃ、９０５Ｄ、９０５Ｅ、９０５Ｆ、９０５Ｇ、９０５Ｈ 半導体素子
９１１ 基材
９１２ 粘着剤層
９１２ｂ 周辺部 910 Dicing die
Claims (10)
- １００℃で１分加熱することにより収縮し、前記加熱前のＭＤ方向の第１長さ１００％に対して前記加熱後の前記ＭＤ方向の第２長さは９５％以下であるダイシングシート。 A dicing sheet that shrinks by heating at 100 ° C. for 1 minute, and the second length in the MD direction after the heating is 95% or less with respect to the first length in the MD direction before the heating of 100%.
- ２３℃で前記ＭＤ方向に３％伸ばしたときの引張応力は１Ｎ／ｍｍ２以上である請求項１に記載のダイシングシート。 2. The dicing sheet according to claim 1, wherein the tensile stress when stretched by 3% in the MD direction at 23 ° C. is 1 N / mm 2 or more.
- ２３℃で前記ＭＤ方向に６％伸ばしたときの引張応力は１．５Ｎ／ｍｍ２以上である請求項１又は２に記載のダイシングシート。 The dicing sheet according to claim 1 or 2, wherein a tensile stress when stretched by 6% in the MD direction at 23 ° C is 1.5 N / mm 2 or more.
- 厚みは４０μｍ～２００μｍである請求項１～３のいずれかに記載のダイシングシート。 4. The dicing sheet according to claim 1, wherein the thickness is 40 μm to 200 μm.
- 基材及び前記基材上に配置された粘着剤層を備える請求項１～４のいずれかに記載のダイシングシート。 The dicing sheet according to any one of claims 1 to 4, further comprising a base material and an adhesive layer disposed on the base material.
- 請求項５に記載のダイシングシートと、
前記粘着剤層上に配置された接着剤層とを備えるダイシング・ダイボンドフィルム。 A dicing sheet according to claim 5;
A dicing die-bonding film comprising: an adhesive layer disposed on the pressure-sensitive adhesive layer. - 前記接着剤層のガラス転移温度は０℃以上である請求項６に記載のダイシング・ダイボンドフィルム。 The dicing / die-bonding film according to claim 6, wherein the adhesive layer has a glass transition temperature of 0 ° C. or higher.
- 前記粘着剤層が、前記接着剤層と接した中央部及び前記中央部の周辺に配置された周辺部を備える請求項６又は７に記載のダイシング・ダイボンドフィルム。 The dicing die-bonding film according to claim 6 or 7, wherein the pressure-sensitive adhesive layer includes a central part in contact with the adhesive layer and a peripheral part disposed around the central part.
- ダイシング・ダイボンドフィルム、及び前記接着剤層上に配置された、改質領域を備える分割ウエハを備える分割体を準備する工程と、
前記ダイシングシートを拡張することにより、前記改質領域を起点に前記分割ウエハ及び前記接着剤層を分断する工程と、
前記分割ウエハ及び前記接着剤層を分断する工程の後に、前記周辺部を加熱する工程とを含む半導体装置の製造方法に使用するための請求項８に記載のダイシング・ダイボンドフィルム。 Preparing a dicing die-bonding film, and a divided body provided with a divided wafer provided with a modified region, disposed on the adhesive layer;
Dividing the divided wafer and the adhesive layer from the modified region by expanding the dicing sheet; and
The dicing die-bonding film according to claim 8, wherein the dicing die-bonding film is used for a semiconductor device manufacturing method including a step of heating the peripheral portion after the step of dividing the divided wafer and the adhesive layer. - 請求項８に記載のダイシング・ダイボンドフィルム、及び前記接着剤層上に配置された、改質領域を備える分割ウエハを備える分割体を準備する工程と、
前記ダイシングシートを拡張することにより、前記改質領域を起点に前記分割ウエハ及び前記接着剤層を分断する工程と、
前記分割ウエハ及び前記接着剤層を分断する工程の後に、前記周辺部を加熱する工程とを含む半導体装置の製造方法。
Preparing a dicing die-bonding film according to claim 8 and a divided body comprising a divided wafer having a modified region disposed on the adhesive layer;
Dividing the divided wafer and the adhesive layer from the modified region by expanding the dicing sheet; and
And a step of heating the peripheral portion after the step of dividing the divided wafer and the adhesive layer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201580067732.5A CN107004589B (en) | 2014-12-12 | 2015-12-10 | Dicing sheet, dicing die-bonding film, and method for manufacturing semiconductor device |
| KR1020177019215A KR102436526B1 (en) | 2014-12-12 | 2015-12-10 | Dicing sheet, dicing/die-bonding film, and method for manufacturing semiconductor device |
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| JP2014252206A JP6445315B2 (en) | 2014-12-12 | 2014-12-12 | Dicing sheet, dicing die-bonding film, and semiconductor device manufacturing method |
| JP2014-252206 | 2014-12-12 |
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| KR (1) | KR102436526B1 (en) |
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2015
- 2015-12-10 WO PCT/JP2015/084644 patent/WO2016093308A1/en active Application Filing
- 2015-12-10 KR KR1020177019215A patent/KR102436526B1/en active IP Right Grant
- 2015-12-10 CN CN201580067732.5A patent/CN107004589B/en active Active
- 2015-12-11 TW TW104141621A patent/TWI667703B/en active
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| JP2009242586A (en) * | 2008-03-31 | 2009-10-22 | Sekisui Film Kk | Adhesive tape substrate and adhesive sheet |
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| CN109906504A (en) * | 2016-11-02 | 2019-06-18 | 琳得科株式会社 | Stealthy adhesive sheet for use in cutting |
| CN109906504B (en) * | 2016-11-02 | 2023-04-14 | 琳得科株式会社 | Adhesive sheet for stealth dicing |
| CN108728003A (en) * | 2017-04-17 | 2018-11-02 | 日东电工株式会社 | Cut die bonding film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016115775A (en) | 2016-06-23 |
| KR102436526B1 (en) | 2022-08-25 |
| JP6445315B2 (en) | 2018-12-26 |
| CN107004589B (en) | 2021-07-16 |
| TW201633389A (en) | 2016-09-16 |
| CN107004589A (en) | 2017-08-01 |
| TWI667703B (en) | 2019-08-01 |
| KR20170095947A (en) | 2017-08-23 |
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