WO2014003056A1 - 半導体装置の製造方法 - Google Patents
半導体装置の製造方法 Download PDFInfo
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- WO2014003056A1 WO2014003056A1 PCT/JP2013/067513 JP2013067513W WO2014003056A1 WO 2014003056 A1 WO2014003056 A1 WO 2014003056A1 JP 2013067513 W JP2013067513 W JP 2013067513W WO 2014003056 A1 WO2014003056 A1 WO 2014003056A1
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- WO
- WIPO (PCT)
- Prior art keywords
- temporary fixing
- semiconductor wafer
- fixing film
- film
- support member
- Prior art date
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Images
Classifications
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- 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
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- 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
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
- H01L2221/6834—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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 used to protect an active side of a device or wafer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
- H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
- H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
- H01L2221/68386—Separation by peeling
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
- H01L25/50—Multistep manufacturing processes of assemblies consisting of devices, each device being of a type provided for in group H01L27/00 or H01L29/00
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to a method for manufacturing a semiconductor device.
- SIP System in Package
- the semiconductor element is required to be as thin as possible.
- Such a semiconductor element is manufactured, for example, by incorporating an integrated circuit into a semiconductor wafer having a certain thickness and then separating the thinned semiconductor wafer by grinding the back surface of the semiconductor wafer. Processing of a semiconductor wafer is performed by temporarily fixing the semiconductor wafer to a support member with a temporary fixing material (see, for example, Patent Documents 1 and 2).
- Patent Document 1 discloses a silicone adhesive
- Patent Document 2 discloses a composition containing rubber as a main component.
- TSV through silicon via
- the temporary fixing material used in the above manufacturing process is required to have adhesiveness for firmly fixing the support member and the semiconductor wafer during grinding of the semiconductor wafer and heat resistance in a high-temperature process.
- the temporary fixing material is required to have releasability so that the processed semiconductor wafer can be easily separated from the support member.
- the semiconductor wafer and the supporting member can be separated at a low temperature so as not to cause the problem of damage and warpage to the semiconductor chip.
- the temporary fixing material described in Patent Document 1 mainly uses a silicone resin, it has poor compatibility with a highly polar monomer such as an acrylate resin or an epoxy resin and is separated during film formation. There is a tendency for the monomer to become uneven and the film formability to deteriorate.
- the temporary fixing material described in Patent Document 2 tends to have insufficient heat resistance for a high-temperature process when a through electrode is formed on a semiconductor wafer and for a high-temperature process when a semiconductor wafer formed with a through-electrode is connected to each other. . If the heat resistance of the temporarily fixing material is insufficient, there is a tendency that the temporarily fixing material is thermally decomposed during the high temperature process and the semiconductor wafer is peeled off from the support member.
- the present invention has been made in view of the above circumstances, and has a low temperature sticking property and sufficient heat resistance capable of sufficiently fixing a semiconductor wafer and a supporting member even when bonded at a low temperature, and after processing. It is an object of the present invention to provide a method for manufacturing a semiconductor device capable of easily separating a semiconductor wafer from a support member.
- an object of the present invention is to provide a method for manufacturing a semiconductor device that can suppress the occurrence of a residue of a temporarily fixed material on a semiconductor wafer.
- a method for manufacturing a semiconductor device is a method for manufacturing a semiconductor device including a semiconductor element obtained by dividing a semiconductor wafer into pieces, and disposing a temporary fixing film between the support member and the semiconductor wafer, Temporary fixing step of temporarily fixing the supporting member and the semiconductor wafer, grinding step of grinding the surface of the semiconductor wafer temporarily fixed to the supporting member on the side opposite to the temporary fixing film, and temporary fixing from the ground semiconductor wafer
- a semiconductor wafer peeling step for peeling the film, and a semiconductor wafer having an edge trimmed on the outer peripheral portion of the surface facing the support member is used as the semiconductor wafer.
- a temporary fixing film is arranged.
- a semiconductor wafer in which edge trimming is performed on the outer peripheral portion of the surface facing the support member is used as the semiconductor wafer.
- positioning the film for temporary fixing between a supporting member and a semiconductor wafer the film for temporary fixing is arrange
- the manufacturing method of the semiconductor device further includes a support member peeling step of peeling the temporarily fixing film from the support member, and the support member is a support in which part or all of the surface facing the temporarily fixing film is subjected to a release treatment. It is preferable to use a member. In this case, the temporary fixing film can be easily peeled off from the support member, and the support member can be reused.
- the mold release treatment may be performed with at least one mold release treatment agent selected from the group consisting of a surface modifier having a fluorine atom, a polyolefin wax, silicone oil, a silicone oil containing a reactive group, and a silicone-modified alkyd resin. preferable.
- the temporary fixing film can be more easily peeled from the support member.
- the film for temporary fixing is obtained by polymerizing an acrylic monomer containing an acrylate monomer having an epoxy group or a methacrylate monomer having an epoxy group, and has a weight average molecular weight of 100,000 or more and a Tg of ⁇ 50 ° C. to 50 ° C. It is preferable to use a film for temporary fixing comprising an epoxy group-containing (meth) acrylic copolymer. In this case, both the low temperature sticking property and the heat resistance of the temporarily fixing film can be achieved.
- a glycidyl acrylate monomer as an acrylate monomer having an epoxy group and a glycidyl methacrylate monomer as a methacrylate monomer having an epoxy group. Also in this case, both the low temperature sticking property and the heat resistance of the temporarily fixing film can be achieved.
- a temporary fixing film containing a release agent made of a silicone-modified alkyd resin is preferably used as the temporary fixing film. In this case, the heat resistance of the temporary fixing film can be ensured, and the temporary fixing film can be easily peeled from the semiconductor wafer.
- the semiconductor wafer and the supporting member can be sufficiently fixed even when bonded at a low temperature, and the semiconductor wafer has a low temperature sticking property and sufficient heat resistance, and the processed semiconductor wafer is easily separated from the supporting member. It is possible to provide a method for manufacturing a semiconductor device that can be used. Moreover, according to this invention, it can suppress that the residue of a temporary fixing material arises in a semiconductor wafer.
- FIG. 1 (A) is a top view showing an embodiment of a film sheet for temporary fixing according to the present invention
- FIG. 1 (B) is a schematic cross-sectional view along the line II in FIG. 1 (A). is there.
- FIG. 2A is a top view showing another embodiment of the film sheet for temporary fixing according to the present invention
- FIG. 2B is a schematic cross-sectional view taken along the line II-II in FIG. It is.
- FIG. 3A is a top view showing another embodiment of the film sheet for temporary fixing according to the present invention
- FIG. 3B is a schematic cross-sectional view taken along the line III-III in FIG. It is. It is a perspective view for demonstrating one Embodiment of the manufacturing method of the semiconductor device which concerns on this invention.
- FIG. 5A, FIG. 5B, and FIG. 5C are schematic cross-sectional views for explaining an embodiment of a method for manufacturing a semiconductor device according to the present invention
- FIG. It is a top view which shows the semiconductor wafer after a process.
- FIG. 7 is a schematic cross-sectional view for explaining a modification of the method for manufacturing the semiconductor device of FIG. 6.
- FIG. 10 is a schematic cross-sectional view for explaining a modification of the method for manufacturing the semiconductor device of FIG. 8.
- FIG. 10 is a schematic cross section for explaining one embodiment of a manufacturing method of a semiconductor device concerning the present invention.
- FIG. 1 (A) is a top view showing an embodiment of a film sheet for temporary fixing according to the present invention
- FIG. 1 (B) is a schematic cross-sectional view along the line II in FIG. 1 (A). is there.
- a temporary fixing film sheet 1 shown in FIG. 1 is provided on the opposite side of the supporting base 10, the temporary fixing film 20 provided on the supporting base 10, and the supporting base 10 of the temporary fixing film 20.
- the protective film 30 is provided.
- the support substrate 10 examples include polyester film, polypropylene film, polyethylene terephthalate film, polyimide film, polyetherimide film, polyether naphthalate film, and methylpentene film.
- the support substrate 10 may be a multilayer film in which two or more kinds of films are combined.
- the support substrate 10 may have a surface treated with a release agent such as silicone or silica.
- the temporary fixing film 20 is obtained by reacting a diamine with an acid dianhydride containing 20 mol% or more of a tetracarboxylic dianhydride represented by the following general formula (I-1) based on the total acid dianhydride.
- a polyimide resin A polyimide resin.
- n represents an integer of 2 to 20.
- the temporary fixing film 20 includes a polyimide resin obtained by the above reaction as a thermoplastic resin having an imide skeleton, thereby sufficiently fixing a member to be processed and a member for supporting the member under a low temperature application condition. Since it can be dissolved using an organic solvent after processing, the processed member and the support member can be easily separated.
- Examples of the tetracarboxylic dianhydride in which n is 2 to 5 in the formula (I-1) include, for example, 1,2- (ethylene) bis (trimellitic dianhydride), 1,3- (trimethylene) bis ( Trimellitate dianhydride), 1,4- (tetramethylene) bis (trimellitate dianhydride), 1,5- (pentamethylene) bis (trimellitate dianhydride).
- Examples of the tetracarboxylic dianhydride in which n is 6 to 20 in the formula (I-1) include 1,6- (hexamethylene) bis (trimellitate dianhydride), 1,7- (heptamethylene) Bis (trimellitic dianhydride), 1,8- (octamethylene) bis (trimellitate dianhydride), 1,9- (nonamethylene) bis (trimellitate dianhydride), 1,10- (decamethylene) bis (trimellitic dianhydride) Anhydride), 1,12- (dodecamethylene) bis (trimellitate dianhydride), 1,16- (hexadecamethylene) bistrimellitate dianhydride, 1,18- (octadecamethylene) bis (trimellitate dianhydride) Thing) etc. are mentioned. These may be used alone or in combination of two or more.
- the tetracarboxylic dianhydride can be synthesized by reacting trimellitic anhydride monochloride with the corresponding diol.
- the amount of the tetracarboxylic dianhydride in the acid dianhydride is preferably 30 mol% or more, more preferably 50 mol% or more, and more preferably 70 mol% or more based on the total acid dianhydride. Even more preferably.
- the polyimide resin according to this embodiment may be obtained using only the tetracarboxylic dianhydride represented by the general formula (I-1) as the acid dianhydride to be reacted with diamine. It may be obtained by using tetracarboxylic dianhydride in combination with another acid dianhydride.
- acid dianhydrides that can be used together with the tetracarboxylic dianhydride of the formula (I-1) include, for example, pyromellitic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride 2,2 ′, 3,3′-diphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-di Carboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2, 3-Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride,
- diamine examples include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, and 3,3′-.
- the acid dianhydride and the diamine represented by the following general formula (A-1) are preferably at least 10 mol%, more preferably at least 20 mol%, still more preferably based on the total diamine. Is preferably obtained by reacting with a diamine containing 30 mol% or more.
- Q 1 , Q 2 and Q 3 each independently represents an alkylene group having 1 to 10 carbon atoms, and p represents an integer of 0 to 10.
- the temporarily fixing film By including a polyimide resin in which the blending amount of the diamine represented by the general formula (A-1) is in the above range, the temporarily fixing film has the characteristics that it has excellent low-temperature sticking property and low stress. Can do. Thereby, it is possible to further easily fix the member sufficiently during the processing while suppressing damage to the temporarily fixed member.
- alkylene group having 1 to 10 carbon atoms examples include groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, propylene, butylene, amylene, hexylene and the like. Can be mentioned.
- the diamine represented by the general formula (A-1) can be used alone or in combination of two or more.
- the polyimide resin according to this embodiment is preferably 3 mol% or more, more preferably 5 mol% or more, and more preferably 5 mol% or more of the acid dianhydride and the diamine represented by the following formula (A-2) with respect to the total diamine.
- it is obtained by reacting with a diamine containing 10 mol% or more.
- the temporary fixing film has characteristics of excellent heat resistance and solubility in an organic solvent. Can do. Thereby, the process of the temporarily fixed member at high temperature and the separation of the processed member and the support member can be further facilitated.
- the acid dianhydride and the diamine represented by the following general formula (A-3) are preferably 3 mol% or more, more preferably 5 mol% or more, based on the total diamine. More preferably, it is obtained by reacting with a diamine containing 10 mol% or more.
- the content of the diamine represented by the following general formula (A-3) is preferably 70 mol% or less with respect to the total diamine.
- R 1 and R 2 each independently represent an alkylene group or phenylene group having 1 to 5 carbon atoms
- R 3 , R 4 , R 5 and R 6 each independently represent 1 to 5 carbon atoms
- 5 represents an alkyl group, a phenyl group or a phenoxy group
- m represents an integer of 1 to 90.
- the temporarily fixing film can be obtained with excellent low temperature sticking properties and low stress. It can. Thereby, it is possible to further easily fix the member sufficiently during the processing while suppressing damage to the temporarily fixed member.
- Examples of the diamine in which m in the general formula (A-3) is 1 include 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane, 1,1,3 , 3-Tetraphenoxy-1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3 , 3-Tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3 , 3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminobutyl) disiloxane, 1,3-dimethyl -1,3-dimethoxy-1,3-bis
- Examples of the diamine in which m is 2 in the general formula (A-3) include 1,1,3,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1, 1,5,5-tetraphenyl-3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5- Bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,5,5-tetra Methyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) Trisiloxane, 1,1,5,
- Examples of the diamine in which m in the general formula (A-3) is 3 to 70 include a diamine represented by the following formula (A-4) and a diamine represented by the following formula (A-5). It is done.
- the diamine represented by the general formula (A-3) can be used alone or in combination of two or more.
- the general formula (A-3) It is preferable to use a siloxane diamine having a phenyl group as part of the side chain of the silicone skeleton as the diamine represented by
- the polyimide resin according to this embodiment can be obtained by subjecting an acid dianhydride containing the tetracarboxylic dianhydride according to the present invention and a diamine to condensation reaction in an organic solvent.
- the acid dianhydride and the diamine are preferably used in equimolar or almost equimolar amounts, and the addition of each component can be performed in any order.
- organic solvent examples include dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphorylamide, m-cresol, o-chlorophenol and the like.
- the reaction temperature is preferably 80 ° C. or lower, more preferably 0 to 50 ° C., and still more preferably 0 to 30 ° C. from the viewpoint of preventing gelation.
- the polyimide resin according to this embodiment can be obtained by dehydrating and ring-closing the reaction product (polyamic acid).
- Dehydration ring closure can be performed using a heat treatment method at 120 ° C. to 250 ° C. or a chemical method.
- the heat treatment at 120 ° C. to 250 ° C. it is preferably carried out while removing water generated by the dehydration reaction out of the system. At this time, water may be removed azeotropically using benzene, toluene, xylene or the like.
- polyimide resin polyimide resin
- the precursor of polyimide includes not only polyamic acid but also partially imidized polyamic acid.
- acetic anhydride, propionic anhydride, benzoic anhydride, carbodiimide compounds such as dicyclohexylcarbodiimide, and the like can be used as the ring-closing agent.
- a ring-closing catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, imidazole or the like may be used.
- the ring-closing agent or the ring-closing catalyst is preferably used in an amount of 1 to 8 moles per 1 mole of the total acid dianhydride.
- the weight average molecular weight of the polyimide resin is preferably from 10,000 to 150,000, more preferably from 30,000 to 120,000, and even more preferably from 50,000 to 100,000, from the viewpoints of improving adhesive strength and improving film moldability.
- the weight average molecular weight of the polyimide resin refers to the weight average molecular weight when measured in terms of polystyrene using high performance liquid chromatography (for example, “HLC-8320GPC” (trade name) manufactured by Tosoh Corporation).
- lithium bromide and phosphoric acid were adjusted to 3.2 g / L and 5.9 g / L, respectively, in a mixed solution in which tetrahydrofuran and dimethyl sulfoxide were mixed at a volume ratio of 1: 1 as a free liquid. It is preferable to use what was mixed and dissolved. Further, TSKgelPack, AW2500, AW3000, and AW4000 manufactured by Tosoh Corporation can be used in combination as a column.
- the polyimide resin preferably has a glass transition temperature (Tg) of ⁇ 20 to 180 ° C., more preferably 0 to 150 ° C., from the viewpoint of reducing heat damage during wafer pressure bonding and film formability. Even more preferred is 150 ° C.
- Tg of the polyimide resin is a peak temperature of tan ⁇ when the film is measured using a viscoelasticity measuring device (manufactured by Rheometric). Specifically, after forming a 30 ⁇ m thick film, it is cut into a size of 10 mm ⁇ 25 mm, and stored under conditions of a heating rate of 5 ° C./min, a frequency of 1 Hz, and a measurement temperature of ⁇ 50 to 300 ° C. Tg is calculated by measuring the temperature dependence of the elastic modulus and tan ⁇ .
- the inorganic fixing filler can be further contained in the temporary fixing film 20.
- the inorganic filler examples include metal fillers such as silver powder, gold powder, and copper powder; non-metallic inorganic fillers such as silica, alumina, boron nitride, titania, glass, iron oxide, and ceramic.
- the inorganic filler can be selected according to the desired function. For example, a metal filler can be added for the purpose of imparting thixotropy to the temporarily fixing film, and a non-metallic inorganic filler can be added for the purpose of imparting a low thermal expansion property and a low hygroscopic property to the temporarily fixing film. Can do.
- the above inorganic fillers can be used alone or in combination of two or more.
- the inorganic filler preferably has an organic group on the surface.
- the surface of the inorganic filler is modified with an organic group, it becomes easy to improve the dispersibility in an organic solvent when forming a temporary fixing film, and the adhesion and heat resistance of the temporary fixing film. .
- the inorganic filler having an organic group on the surface can be obtained, for example, by mixing a silane coupling agent represented by the following general formula (B-1) and an inorganic filler and stirring at a temperature of 30 ° C. or higher. . It can be confirmed by UV measurement, IR measurement, XPS measurement or the like that the surface of the inorganic filler is modified with an organic group.
- X represents an organic group selected from the group consisting of a phenyl group, a glycidoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, a vinyl group, an isocyanate group, and a methacryloxy group;
- R 11 , R 12 and R 13 each independently represents an alkyl group having 1 to 10 carbon atoms.
- alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group and the like. Can be mentioned. A methyl group, an ethyl group, and a pentyl group are preferable because they are easily available.
- X is preferably an amino group, a glycidoxy group, a mercapto group or an isocyanate group, more preferably a glycidoxy group or a mercapto group, from the viewpoint of heat resistance.
- s is preferably from 0 to 5, and more preferably from 0 to 4, from the viewpoint of suppressing film fluidity at high heat and improving heat resistance.
- Preferred silane coupling agents include, for example, trimethoxyphenylsilane, dimethyldimethoxyphenylsilane, triethoxyphenylsilane, dimethoxymethylphenylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N -(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-isocyanatopropyl
- 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-mercaptopropyltrimethoxysilane are preferable, and trimethoxyphenylsilane, 3-glycidoxy More preferred are propyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.
- a silane coupling agent can be used alone or in combination of two or more.
- the amount of the coupling agent used is preferably 0.01 to 50 parts by weight, and 0.05 parts by weight with respect to 100 parts by weight of the inorganic filler, from the viewpoint of balancing the effect of improving heat resistance and storage stability. Part to 20 parts by weight is more preferable, and from the viewpoint of improving heat resistance, 0.5 to 10 parts by weight is even more preferable.
- the content thereof is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and more preferably 100 parts by mass or less with respect to 100 parts by mass of the polyimide resin. Even more preferred.
- the minimum of content of an inorganic filler does not have a restriction
- An organic filler can be further blended in the temporary fixing film according to the present embodiment.
- the organic filler include carbon, rubber filler, silicone fine particles, polyamide fine particles, and polyimide fine particles.
- the film for temporary fixing according to the present embodiment can further contain a radical polymerizable compound having a carbon-carbon unsaturated bond and a radical generator.
- radical polymerizable compound having a carbon-carbon unsaturated bond examples include compounds having an ethylenically unsaturated group.
- Examples of the ethylenically unsaturated group include vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadiimide group, (meth) acryloyl group and the like from the viewpoint of reactivity. , (Meth) acryloyl groups are preferred.
- the radical polymerizable compound is preferably a bifunctional or higher functional (meth) acrylate from the viewpoint of reactivity.
- acrylates include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, and trimethylolpropane.
- Triacrylate trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate , Pentaerythritol triacrylate, pentaerythritol tetraacrylate Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryl
- R 21 and R 22 each independently represent a hydrogen atom or a methyl group.
- a compound having a tricyclodecane skeleton as represented by the general formula (C-1) is preferable in that it can improve the solubility and adhesiveness of the temporarily fixing film after curing.
- urethane acrylate, urethane methacrylate, isocyanuric acid di / triacrylate and isocyanuric acid di / trimethacrylate are preferred in that the adhesiveness of the temporarily fixing film after curing can be improved.
- the temporary fixing film contains a trifunctional or higher functional acrylate compound as a radical polymerizable compound, the adhesiveness of the cured temporary fixing film can be further improved and the outgassing during heating can be suppressed.
- the film for temporary fixing contains isocyanuric acid di / triacrylate and / or isocyanuric acid di / trimethacrylate as a radical polymerizable compound in that the heat resistance of the film for temporary fixing after curing is further improved.
- Radical polymerizable compounds can be used singly or in combination of two or more.
- radical generator examples include a thermal radical generator and a photo radical generator.
- a thermal radical generator such as an organic peroxide.
- organic peroxides examples include 2,5-dimethyl-2,5-di (t-butylperoxyhexane), dicumyl peroxide, t-butylperoxy-2-ethylhexanate, and t-hexyl.
- Peroxy-2-ethylhexanate 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5- And trimethylcyclohexane, bis (4-t-butylcyclohexyl) peroxydicarbonate, and the like.
- the organic peroxide is selected in consideration of conditions (for example, film forming temperature), curing (bonding) conditions, other process conditions, storage stability, and the like when the temporary fixing film is formed.
- the organic peroxide used in the present embodiment preferably has a one minute half-life temperature of 120 ° C. or higher, more preferably 150 ° C. or higher.
- examples of such an organic peroxide include perhexa 25B (manufactured by NOF Corporation), 2,5-dimethyl-2,5-di (t-butylperoxyhexane) (1 minute half-life temperature: 180 ° C. ), Park mill D (manufactured by NOF Corporation), dicumyl peroxide (1 minute half-life temperature: 175 ° C.), and the like.
- the radical generator can be used alone or in combination of two or more.
- the content of the radical polymerizable compound in the temporary fixing film improves the retention of the member (eg, semiconductor wafer) during processing while ensuring sufficient solubility of the temporary fixing film after curing, that is, releasability of the member.
- the amount is preferably 0 to 100 parts by mass, more preferably 3 to 50 parts by mass, and still more preferably 5 to 40 parts by mass with respect to 100 parts by mass of the polyimide resin.
- the content of the radical generator in the temporarily fixing film is 0.01 to 20 masses with respect to 100 mass parts of the total amount of the radical polymerizable compound from the viewpoint of achieving both curability, suppression of outgassing and storage stability. Part is preferred, 0.1 to 10 parts by weight is more preferred, and 0.5 to 5 parts by weight is even more preferred.
- the temporary fixing film of the present embodiment can further contain an epoxy resin as a thermosetting compound different from the above-mentioned radical polymerizable compound.
- an epoxy resin curing agent and a curing accelerator may be further blended.
- Examples of the epoxy resin include compounds containing at least two epoxy groups in the molecule, and phenol glycidyl ether type epoxy resins are preferably used from the viewpoint of curability and cured product characteristics.
- Such resins include bisphenol A, bisphenol AD, bisphenol S, bisphenol F or condensates of halogenated bisphenol A and epichlorohydrin, glycidyl ether of phenol novolac resin, glycidyl ether of cresol novolac resin, glycidyl of bisphenol A novolak resin.
- Examples include ether. Two or more of these can be used in combination.
- the compounding amount of the epoxy resin is preferably 1 to 100 parts by mass and more preferably 5 to 60 parts by mass with respect to 100 parts by mass of the polyimide resin.
- the blending amount of the epoxy resin is within the above range, it is possible to sufficiently reduce the workability due to the time required for etching while ensuring sufficient adhesiveness.
- Examples of the epoxy resin curing agent include a phenol resin and an amine compound. It is preferable to use a phenol resin from the viewpoints of storage stability, outgassing during curing, and compatibility with the resin.
- the blending amount of the curing agent is preferably adjusted according to the epoxy equivalent, and is preferably 10 to 300 parts by mass, more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the epoxy resin.
- the blending amount of the curing agent is within the above range, heat resistance can be easily ensured.
- curing accelerator examples include imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole-tetraphenylborate, 1,8-diazabicyclo [5. 4.0] undecene-7-tetraphenylborate and the like. Two or more of these can be used in combination.
- the blending amount of the curing accelerator is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin.
- the blending amount of the curing accelerator is within the above range, it is possible to sufficiently reduce the storage stability while obtaining sufficient curability.
- an epoxy resin may be blended as a thermosetting compound, or a radical polymerizable compound and an epoxy resin may be blended together.
- the content of the epoxy resin is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and more preferably 30 parts by mass with respect to 100 parts by mass of the radical polymerizable compound from the viewpoint of achieving both solubility and heat resistance. Even more preferred is part or less.
- the temporary fixing film preferably further contains at least one selected from the group consisting of a surface modifier having a fluorine atom, a polyolefin wax, and silicone oil, from the viewpoint of improving solubility in an organic solvent.
- Examples of the surface modifier having a fluorine atom include Mega-Fac (manufactured by DIC, trade name), Hypertech (manufactured by Nissan Chemical, trade name), Optool (manufactured by Daikin, trade name), and Cheminox (manufactured by Unimatec, trade name). ) Etc. can be used.
- polyolefin waxes examples include polyethylene, amide, and montanic acid waxes.
- silicone oil examples include straight silicone oil (KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd.)), reactive silicone oil (X-22-176F, X-22-3710, X-22-173DX, X-22-170BX). (Manufactured by Shin-Etsu Chemical Co., Ltd.).
- Fluorine-based surface modifier, polyolefin wax and silicone oil can be used alone or in combination of two or more.
- the content of the fluorine-based surface modifier and the polyolefin wax in the temporary fixing film is preferably 0.01 to 10 parts by mass in total with respect to 100 parts by mass of the polyimide resin, from the viewpoint of the balance between solubility and adhesiveness. 0.1 to 5 parts by mass is more preferable, and 0.5 to 3 parts by mass is even more preferable.
- the temporary fixing film 20 is obtained by polymerizing a monomer containing a functional monomer such as an acrylate having an epoxy group or a methacrylate having an epoxy group, and has a weight average molecular weight.
- a functional monomer such as an acrylate having an epoxy group or a methacrylate having an epoxy group
- acrylic copolymer an epoxy group-containing (meth) acrylic copolymer (hereinafter referred to as “acrylic copolymer”) having 100,000 or more.
- acrylic copolymer an epoxy group-containing (meth) acrylic copolymer having 100,000 or more.
- acrylic copolymer for example, (meth) acrylic acid ester copolymer and acrylic rubber can be used, and acrylic rubber is preferably used.
- Examples of the acrylate having an epoxy group include glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl acrylate.
- Examples of the methacrylate having an epoxy group include glycidyl methacrylate, 4-hydroxybutyl methacrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl methacrylate.
- glycidyl acrylate and glycidyl methacrylate are preferable from the viewpoint of heat resistance.
- Acrylic rubber is a rubber mainly composed of an acrylic ester and made of, for example, a copolymer of butyl acrylate and acrylonitrile, a copolymer of ethyl acrylate and acrylonitrile, or the like.
- the Tg of the acrylic copolymer is preferably -50 ° C to 50 ° C.
- the Tg of the acrylic copolymer is 50 ° C. or less, the flexibility of the temporary fixing film 20 can be ensured, and a decrease in low-temperature pressure-bonding property can be suppressed. Further, when bumps or the like are present on the semiconductor wafer, it is easy to embed bumps at 150 ° C. or lower.
- the Tg of the acrylic copolymer is ⁇ 50 ° C. or more, it is possible to suppress a decrease in handleability and peelability due to the flexibility of the temporary fixing film 20 becoming too high.
- the Tg of the acrylic copolymer is the peak temperature of tan ⁇ when the acrylic copolymer film is measured using a viscoelasticity measuring device (manufactured by Rheometric). Specifically, after forming a 30 ⁇ m thick film, it is cut into a size of 10 mm ⁇ 25 mm, and stored under conditions of a heating rate of 5 ° C./min, a frequency of 1 Hz, and a measurement temperature of ⁇ 50 to 300 ° C. Tg is calculated by measuring the temperature dependence of the elastic modulus and tan ⁇ .
- the weight average molecular weight of the acrylic copolymer is preferably 100,000 or more and 1,000,000 or less.
- a weight average molecular weight is a polystyrene conversion value using the calibration curve by a standard polystyrene by the gel permeation chromatography method (GPC).
- the amount of the acrylate having an epoxy group or the methacrylate having an epoxy group contained in the acrylic copolymer is preferably 0.1 to 20% by mass in a blending mass ratio at the time of copolymer synthesis. More preferably, it is ⁇ 15% by mass, and further preferably 0.5 ⁇ 10% by mass. When the blending mass ratio is within the above range, it is possible to suppress a decrease in flexibility while obtaining sufficient heat resistance.
- acrylic copolymer As the acrylic copolymer as described above, one obtained by a polymerization method such as pearl polymerization or solution polymerization may be used, or HTR-860P (trade name, manufactured by Nagase ChemteX Corporation) is available. You may use anything.
- a polymerization method such as pearl polymerization or solution polymerization
- HTR-860P trade name, manufactured by Nagase ChemteX Corporation
- the temporary fixing film 20 may contain a curing accelerator that accelerates curing of the epoxy group contained in the acrylic copolymer.
- curing accelerator examples include imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole-tetraphenylborate, 1,8-diazabicyclo [5. 4.0] undecene-7-tetraphenylborate and the like. Two or more of these can be used in combination.
- the blending amount of the curing accelerator is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the acrylic copolymer.
- the blending amount of the curing accelerator is within the above range, it is possible to sufficiently reduce the storage stability while obtaining sufficient curability.
- the temporary fixing film 20 preferably contains a silicone-modified alkyd resin.
- a silicone-modified alkyd resin for example, (i) a normal synthesis reaction for obtaining an alkyd resin, that is, when reacting a polyhydric alcohol with a fatty acid, a polybasic acid, etc., the organopolysiloxane is simultaneously reacted as an alcohol component (Ii)
- a method in which a general alkyd resin synthesized in advance is reacted with an organopolysiloxane and either method (i) or (ii) can be used.
- Examples of the polyhydric alcohol used as a raw material for the alkyd resin include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, and neopentyl glycol, glycerin, trimethylolethane, Examples thereof include trihydric alcohols such as trimethylolpropane, and tetrahydric or higher polyhydric alcohols such as diglycerin, triglycerin, pentaerythritol, dipentaerythritol, mannitol, and sorbit. These may be used individually by 1 type and may be used in combination of 2 or more type.
- polybasic acid used as a raw material for the alkyd resin examples include aromatic polybasic acids such as phthalic anhydride, terephthalic acid, isophthalic acid, and trimetic anhydride, and aliphatic saturated polybasic acids such as succinic acid, adipic acid, and sebacic acid.
- Aliphatic unsaturated polybasic acids such as basic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic anhydride, cyclopentadiene-maleic anhydride adduct, terpene-maleic anhydride adduct, rosin-maleic anhydride
- polybasic acids by Diels-Alder reaction such as acid adducts. These may be used individually by 1 type and may be used in combination of 2 or more type.
- the alkyd resin may further contain a modifying agent or a crosslinking agent.
- the modifier examples include octylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid, dehydrated ricinoleic acid, or coconut oil, linseed oil, kiri oil, castor Oil, dehydrated castor oil, soybean oil, safflower oil, and these fatty acids can be used. These may be used individually by 1 type and may be used in combination of 2 or more type.
- crosslinking agent examples include amino resins such as melamine resins and urea resins, urethane resins, epoxy resins, and phenol resins. Among these, amino resins are particularly preferably used. In this case, an aminoalkyd resin cross-linked with an amino resin is preferably obtained.
- a crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type.
- an acidic catalyst can be used as a curing catalyst.
- an acidic catalyst It can select suitably from well-known acidic catalysts as a crosslinking reaction catalyst of an alkyd resin, and can use it.
- an acidic catalyst for example, an organic acidic catalyst such as p-toluenesulfonic acid and methanesulfonic acid is suitable.
- An acidic catalyst may be used individually by 1 type, and may be used in combination of 2 or more type.
- the blending amount of the acidic catalyst is usually 0.1 to 40 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight as the total of the alkyd resin and the crosslinking agent. It is selected in the range.
- silicone-modified alkyd resin examples include Tesfine TA31-209E (trade name, manufactured by Hitachi Chemical Co., Ltd.).
- the temporary fixing film 20 contains a silicone-modified alkyd resin
- the temporary fixing film can be easily peeled off at a low temperature of 100 ° C. or less without using a solvent.
- the compounding amount of the silicone-modified alkyd resin is preferably 5 to 50 parts by mass and more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the acrylic copolymer.
- the blending amount of the silicone-modified alkyd resin is within the above range, it is possible to achieve both adhesiveness and peelability after processing when processing a semiconductor wafer.
- the temporary fixing film 20 can be formed by the following procedure.
- a varnish is prepared by mixing and kneading the above-described polyimide resin, and if necessary, an inorganic filler, a radical polymerizable compound, a radical generator and other components in an organic solvent.
- Mixing and kneading can be carried out by appropriately combining dispersers such as a normal stirrer, a raking machine, a three-roller, and a ball mill.
- Mixing and kneading in the case of blending the inorganic filler can also be performed by appropriately combining dispersers such as ordinary stirrers, raking machines, three-rollers, and ball mills.
- the temporary fixing film 20 contains an acrylic copolymer, an acrylic copolymer, a silicone-modified alkyd resin and a curing accelerator are mixed and kneaded in the same manner as described above to prepare a varnish.
- Examples of the organic solvent used for preparing the varnish include dimethylformamide, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, dioxane, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, and N- And methyl-pyrrolidinone.
- the temporarily fixed film 20 can be formed by coating the varnish obtained above on the support substrate 10 to form a varnish layer and drying by heating.
- the varnish layer When the radical polymerizable compound and the radical generator are blended, it is preferable to dry the varnish layer at a temperature at which the radical polymerizable compound does not sufficiently react during drying and under conditions where the solvent is sufficiently evaporated.
- the varnish layer When a curing accelerator is blended with the acrylic copolymer, it is preferable to dry the varnish layer under a temperature at which the epoxy group does not sufficiently react during drying and under conditions where the solvent is sufficiently volatilized.
- the temperature at which the radical polymerizable compound does not sufficiently react is specifically determined by using DSC (for example, “DSC-7 type” (trade name) manufactured by PerkinElmer Co., Ltd.) / Min, measurement atmosphere: can be set below the peak temperature of the heat of reaction when DSC measurement is performed under the conditions of air.
- DSC for example, “DSC-7 type” (trade name) manufactured by PerkinElmer Co., Ltd.
- the varnish layer it is preferable to dry the varnish layer by heating at 60 to 180 ° C. for 0.1 to 90 minutes, for example.
- the thickness of the temporary fixing film 20 is preferably 1 to 300 ⁇ m from the viewpoint of both ensuring the function of temporary fixing and suppressing the residual volatile matter described later.
- a previously formed film of 100 ⁇ m or less may be bonded.
- the residual solvent when the thick film is produced can be reduced, and the possibility of contamination by volatile components can be sufficiently reduced.
- the residual volatile content of the temporarily fixing film is 10% or less. In this case, it is possible to prevent voids from being generated inside the film and impair processing reliability, and sufficiently reduce the possibility of contamination of peripheral materials or processed members due to volatile components during processing including heating. can do.
- the protective film 30 is further laminated to obtain the temporary fixing film sheet 1, but the supporting substrate 10 is removed from the formed temporary fixing film 20. Only the film for temporary fixing can be produced by removing the film. From the viewpoint of preservability, it is preferable to form the sheet without removing the support substrate 10.
- Examples of the protective film 30 include polyethylene, polypropylene, and polyethylene terephthalate.
- the temporary fixing film according to the present invention can be appropriately changed according to use.
- FIG. 2A is a top view showing another embodiment of the film sheet for temporary fixing according to the present invention
- FIG. 2B is a schematic cross-sectional view taken along the line II-II in FIG. It is.
- the temporarily fixing film sheet 2 shown in FIG. 2 has the same configuration as the temporarily fixing film sheet 1 except that the temporarily fixing film 20 and the protective film 30 are cut in advance according to the shape of the temporarily fixed member.
- the temporary fixing film sheet 2 has an advantage that it is not necessary to cut the film into a wafer shape after lamination.
- FIG. 3 (A) is a top view showing still another embodiment of the film sheet for temporary fixing according to the present invention
- FIG. 3 (B) is a schematic cross section taken along line III-III of FIG. 3 (A).
- the temporary fixing film sheet 3 shown in FIG. 3 is temporary except that the low adhesive force layer 40 having a low adhesive force surface whose adhesive force is smaller than that of the surrounding surface is formed on both surfaces of the temporary fixing film 20. It has the same configuration as the fixing film sheet 1.
- the low adhesion layer 40 may be provided only on one side of the temporary fixing film 20. Further, the temporary fixing film sheet 3 may be processed as shown in FIG. In this case, the shape of the low adhesion layer 40 may be the same as or smaller than the shape of the cut temporary fixing film 20.
- the low adhesion layer 40 for example, a varnish containing at least one of the above-described surface modifier having fluorine atoms, polyolefin wax, and silicone oil is applied to a predetermined portion of the support substrate 10. After drying and then forming the temporary fixing film 20, it can be formed by applying again to a predetermined portion of the temporary fixing film 20 and drying. Moreover, after forming a low-adhesion film from a varnish containing at least one of the above-described surface modifier having a fluorine atom, polyolefin wax, and silicone oil on a base material in advance, the film is temporarily fixed.
- the low adhesion layer 40 can also be provided by laminating on both sides of 20.
- a temporary fixing film 20 is prepared.
- the temporary fixing film 20 is pasted onto a circular support member 60 made of glass or a wafer by a roll laminator 50. After pasting, the temporary fixing film is cut into a circle according to the shape of the support member. At this time, it is preferable to set the shape to be cut in accordance with the shape of the semiconductor wafer to be processed.
- the temporary fixing film 20 is used in the present embodiment, the temporary fixing film 20 is prepared, and after the protective film 30 is peeled off, the temporary fixing film 20 is peeled off while the supporting base material 10 is peeled off. You may affix on 60. Moreover, when using the film sheet 2 for temporary fixing mentioned above, a cutting process can be skipped.
- a vacuum laminator may be used for attaching the temporary fixing film to the support member. Moreover, you may affix the film for temporary fixing on the semiconductor wafer side to process instead of a supporting member.
- a support member bonded with a temporary fixing film is set on a vacuum press or a vacuum laminator, and the semiconductor wafer is pressed and pasted with a press.
- a wafer on which the film for temporarily fixing is pasted is set on a vacuum press or a vacuum laminator, and the support member is pressed and pasted.
- the pressure is 1 hPa or less, the pressure is 1 MPa, the pressure is 120 ° C. to 200 ° C., and the holding time is 100 seconds to 300 seconds. Then, a temporary fixing film 20 is attached.
- a vacuum laminator for example, a vacuum laminator LM-50 ⁇ 50-S manufactured by NPC Co., Ltd., a vacuum laminator V130 manufactured by Nichigo Morton Co., Ltd. is used, and the pressure is 1 hPa or less, and the pressure bonding temperature is 60 ° C. to 180 ° C.
- the film for temporary fixing is preferably 80 ° C. to 150 ° C., laminating pressure 0.01 to 0.5 Mpa, preferably 0.1 to 0.5 Mpa, holding time 1 second to 600 seconds, preferably 30 seconds to 300 seconds. 20 is pasted.
- the temporary fixing film 20 is interposed between the support member 60 and the semiconductor wafer 70 to temporarily fix the semiconductor wafer 70 to the support member 60.
- the support member and the semiconductor wafer can be fixed while sufficiently preventing damage to the semiconductor wafer.
- the support member 60 has a release treatment surface 62 on the surface.
- the release treatment surface 62 is formed by releasing a part of the surface of the support member 60 with a release treatment agent.
- a mold release treatment agent for example, polyethylene wax, fluorine wax, or the like can be used.
- a mold release treatment method for example, dip, spin coating, vacuum deposition, or the like can be used.
- a surface modifier having fluorine atoms, polyolefin wax, silicone oil, silicone oil containing a reactive group, or silicone-modified alkyd resin can be used.
- Examples of the surface modifier having a fluorine atom include MegaFac (manufactured by DIC Corporation, trade name), Hypertech (manufactured by Nissan Chemical Industries, trade name), OPTOOL (manufactured by Daikin Industries, Ltd.), Commercial products such as trade name) and Cheminox (trade name, manufactured by Unimatec Co., Ltd.) can be used.
- polyolefin wax examples include polyethylene wax, amide wax, and montanic acid wax.
- silicone oil examples include straight silicone oil (for example, KF-96 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)) and reactive silicone oil (for example, X-22-176F, X-22-3710, X-22). -173DX, X-22-170BX (manufactured by Shin-Etsu Chemical Co., Ltd., trade name)).
- silicone-modified alkyd resin examples include those similar to the silicone-modified alkyd resin used for the temporary fixing film.
- mold release treatment agents can be used singly or in combination of two or more.
- a release layer may be formed by applying a varnish containing a release treatment agent on the temporary fixing film 20.
- the release treatment is performed on the center of the support member 60 and not on the edge. By doing so, it is possible to shorten the dissolution time when the temporary fixing film is dissolved with an organic solvent after the processing while securing the adhesive strength with the temporary fixing film during the processing of the semiconductor wafer.
- the semiconductor wafer 70 has a disk shape with edge trimming, and the side of the semiconductor wafer 70 having the edge trimming 75 and the support member 60 are more than the side having the edge trimming of the semiconductor wafer.
- a semiconductor wafer is temporarily fixed to the support member by interposing a temporary fixing film 20 having a small diameter. Further, a predetermined wiring pattern is processed on the semiconductor wafer 70, and a temporary fixing film is bonded to the surface having the wiring pattern.
- Edge trimming 75 is applied to the outer peripheral portion of the surface of the semiconductor wafer 70 facing the support member 60.
- the film 20 for temporary fixing which has circular planar shape, for example is used.
- the radius of the temporary fixing film 20 is smaller by the length D than the radius of the surface of the semiconductor wafer 70 facing the support member 60.
- the temporary fixing film 20 is arranged so that the center of the surface of the semiconductor wafer 70 facing the support member 60 and the center of the temporary fixing film 20 coincide. That is, the temporary fixing film 20 is disposed on the inner side by a length D than the edge trimming 75 portion.
- the back surface of the semiconductor wafer (in this embodiment, the side opposite to the side having the edge trimming of the semiconductor wafer (the side having the wiring pattern) is ground by the grinder 90, For example, the thickness of about 700 ⁇ m is reduced to 100 ⁇ m or less.
- the grinding conditions can be arbitrarily selected according to the desired thickness and grinding state of the semiconductor wafer.
- edge trimming is applied to a semiconductor wafer, it becomes easy to suppress damage to the wafer during the wafer grinding process.
- the shape of the temporarily fixing film smaller than the side having the edge trimming of the semiconductor wafer, it is possible to prevent the temporarily fixing film from protruding from the ground wafer. It is possible to prevent the residue of the film from being generated and contaminating the semiconductor wafer.
- the temporary fixing film 20 is disposed inward by the length D from the edge trimming 75 portion, and the length D is preferably 1 mm or more and 2 mm or less.
- the length D is 1 mm or more, even if an error occurs at the position where the temporary fixing film 20 is disposed, the temporary fixing film 20 is difficult to protrude from the edge trimming 75 portion.
- the length D is 2 mm or less, the flatness of the semiconductor wafer 70 can be ensured, and the semiconductor wafer 70 can be satisfactorily ground in the subsequent grinding step.
- a process such as dry ion etching or a Bosch process is performed on the back surface side of the thinned semiconductor wafer 80 to form a through hole, and then a process such as copper plating is performed to form a through electrode 82 (FIG. 5 ( See C)).
- FIG. 5D is a top view of the processed semiconductor wafer.
- the processed semiconductor wafer 80 is separated from the support member 60 and further separated into semiconductor elements by dicing along a dicing line 84.
- a semiconductor device is obtained by connecting the obtained semiconductor element to another semiconductor element or a semiconductor element mounting substrate.
- a semiconductor device can be obtained by stacking a plurality of semiconductor wafers or semiconductor elements obtained through the same process as described above so that the through electrodes are connected to each other.
- the stacked body can be cut by dicing to obtain a semiconductor device.
- a thick film semiconductor wafer in which a through electrode has been previously prepared is prepared, a temporary fixing film is bonded to the circuit surface of the wafer, and the back surface of the semiconductor wafer (in this embodiment, the semiconductor wafer)
- the side having the edge trimming can be ground to reduce the thickness of, for example, about 700 ⁇ m to 100 ⁇ m or less.
- the thinned semiconductor wafer is etched to cue the through electrode, thereby forming a passivation film.
- the copper electrode is cueed again by ion etching or the like to form a circuit.
- a semiconductor wafer thus processed can be obtained.
- Separation of the processed semiconductor wafer 80 and the support member 60 can be easily performed by bringing an organic solvent into contact with the temporary fixing film 20 to dissolve a part or all of the temporary fixing film 20.
- the semiconductor wafer 80 processed from the support member 60 by dissolving the temporarily fixing film 20 up to the release treatment surface 62 of the support member 60. Can be separated. In this case, the processing time required for separation can be shortened.
- organic solvent examples include N-methyl-2pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether (diglyme), cyclohexanone, trimethylammonium hydroxide (TMAH), and one or more of these, A mixed solvent with at least one of triethanolamine and alcohols can be used.
- the organic solvent may be composed of one kind of compound or a mixture of two or more kinds of compounds.
- Preferred examples of the solvent include NMP, NMP / ethanolamine, NMP / TMAH aqueous solution, NMP / triethanolamine, (NMP / TMAH aqueous solution) / alcohol, and TMAH aqueous solution / alcohol.
- Examples of the method of bringing the organic solvent into contact with the temporary fixing film 20 include immersion, spray cleaning, and ultrasonic cleaning.
- the temperature of the organic solvent is preferably 25 ° C. or higher, more preferably 40 ° C. or higher, and even more preferably 60 ° C. or higher.
- the contact time with the organic solvent is preferably 1 minute or longer, more preferably 10 minutes or longer, and even more preferably 30 minutes or longer.
- Separation of the semiconductor wafer 80 and the support member 60 is performed, for example, by placing a jig having a key shape on the interface between the temporary fixing film and the release treatment surface and applying stress upward. be able to.
- the mold release surface 62 is formed on a part of the surface of the support member 60.
- the mold release surface 62a is formed on the entire surface of the support member 60a. May be.
- the semiconductor wafer 80 processed mechanically from the support member 60 at room temperature can be easily separated without using a solvent.
- a De-Bonding device EVG805EZD manufactured by EVG is used for mechanical separation.
- the mold release surface 62a is formed by applying a surface modifier having fluorine atoms to the entire surface of the support member 60a, for example, by spin coating.
- a surface modifier having fluorine atoms for example, by spin coating.
- a spin coater MS-A200 manufactured by Mikasa Co., Ltd. a fluorine type mold release agent (OPTOOL HD-100Z) manufactured by Daikin Industries, Ltd. on the surface of the support member 60a at 1000 rpm to 2000 rpm for 10 seconds to 30 seconds. Is applied, and then left in an oven set at 120 ° C. for 3 minutes to volatilize the solvent and form a release treatment surface 62a.
- FIG. 1 An example of temporarily fixing, processing, and separating a semiconductor wafer using the temporarily fixing film sheet 3 is shown in FIG.
- the temporarily fixing film 20 is bonded to the side having the edge trimming of the semiconductor wafer 70 on which the edge trimming 75 has been performed, thereby preparing the semiconductor wafer 100 with the temporarily fixing film (FIG. 8A). .
- the semiconductor wafer 100 with a temporary fixing film is set on a vacuum press or a vacuum laminator, and the support member 60 is pressed and pasted with a press.
- the temporary fixing film 20 having the low adhesion layer 40 on both sides is interposed between the support member 60 and the semiconductor wafer 70, and the semiconductor wafer 70 is temporarily attached to the support member 60. Fix it.
- the back surface of the semiconductor wafer is ground (FIG. 8C), and further processing such as circuit formation and through hole formation is performed.
- an organic solvent is brought into contact with the temporarily fixing film 20 to dissolve a part of the temporarily fixing film 20.
- the processed semiconductor wafer 80 can be separated from the support member 60 by dissolving the temporarily fixing film 20 to the low adhesive layer 40. Also in this case, the processing time required for separation can be shortened.
- the processed semiconductor wafer 80 has through electrodes formed in the same manner as described above, and is separated into semiconductor elements by dicing.
- the low adhesion layer 40 is formed on a part of the surface of the temporary fixing film 20, but the low adhesion layer 40a is formed on the surface of the temporary fixing film 20, as shown in FIG. It may be formed in the whole.
- the semiconductor wafer 80 processed mechanically from the support member 60 at room temperature can be easily separated without using a solvent.
- a De-Bonding device EVG805EZD manufactured by EVG is used for mechanical separation.
- the through electrode 86 is formed by the above-described method, and the semiconductor element 110 is obtained as a single piece (FIG. 10A).
- a plurality of semiconductor elements 110 are stacked on the wiring substrate 120, for example.
- the semiconductor device 200 including the semiconductor element 110 can be obtained (FIG. 10B).
- polyimide resin PI-3 While cooling the flask in an ice bath, 26.11 g (0.05 mol) of decamethylene bistrimellitic acid dianhydride (DBTA) was added little by little to the solution in the flask. After completion of the addition, the solution was heated to 180 ° C. while blowing nitrogen gas and kept for 5 hours to obtain polyimide resin PI-3.
- the weight average molecular weight of polyimide resin PI-3 was 70000, and Tg was 100 ° C.
- APB-N molecular weight 292.34
- side chain phenyl group-containing long-chain siloxane diamine manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-1660B-3, molecular weight: 4400
- 22 g 0.005 mol
- 100 g of N-methyl-2-pyrrolidone (NMP) as a solvent were charged and stirred to dissolve the diamine in the solvent.
- polyimide resin PI-4 While cooling the flask in an ice bath, 26.11 g (0.05 mol) of decamethylene bistrimellitic acid dianhydride (DBTA) was added little by little to the solution in the flask. After completion of the addition, the solution was heated to 180 ° C. while blowing nitrogen gas, and kept for 5 hours to obtain polyimide resin PI-4.
- the weight average molecular weight of polyimide resin PI-2 was 70000, and Tg was 160 ° C.
- polyimide resin PI-5 While cooling the flask in an ice bath, 10.90 g (0.05 mol) of pyromellitic anhydride was added little by little to the solution in the flask. After completion of the addition, the solution was heated to 180 ° C. while blowing nitrogen gas and kept for 5 hours to obtain polyimide resin PI-5.
- the weight average molecular weight of polyimide resin PI-5 was 30000, and Tg was 200 ° C.
- Table 1 shows the compositions (mol% based on the total amount of anhydride or diamine) of polyimide resins PI-1 to PI-5.
- Examples 1 to 14, Comparative Examples 1 and 2 [Preparation of varnish] Based on the compositions shown in Tables 2 to 4 (units are parts by mass), each material was dissolved and mixed in an NMP solvent so that the solid content concentration was 50% by mass to prepare varnishes for forming films. .
- SK Dyne 1435 Acrylic adhesive (manufactured by Soken Chemical)
- A-DCP Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
- A-9300 Ethoxylated isocyanuric acid triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
- A-DOG 1,10-decanediol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
- UA-512 Bifunctional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
- YDF-8170 Bisphenol F type bisglycidyl ether (manufactured by Toto Kasei)
- VG-3101 High heat resistant trifunctional epoxy resin (manufactured by Printec) Park Mill D: Dicumyl peroxide (manufactured by NOF) H27
- a temporary fixing film is rolled (temperature 150 ° C., linear pressure 4 kgf / cm, feed rate 0) on the back surface (surface opposite to the support table) of the silicon wafer (6 inch diameter, thickness 400 ⁇ m) placed on the support table. .5 m / min) to form a laminate.
- the PET film was peeled off, and a polyimide film “Upilex” (trade name) having a thickness of 80 ⁇ m, a width of 10 mm, and a length of 40 mm was pressed and laminated on the temporary fixing film under the same conditions as described above.
- the sample prepared in this manner was subjected to a 90 ° peel test at room temperature using a rheometer “Strograph ES” (trade name) to measure the peel strength between the temporary fixing film and Upilex. .
- a sample having a peel strength of 2 N / cm or more was designated as A, and a sample having a peel strength of less than 2 N / cm was designated as C.
- a film for temporary fixing is rolled (temperature 80 ° C., linear pressure 4 kgf / cm, feed rate 0) on the back surface (surface opposite to the support table) of a silicon wafer (6 inch diameter, thickness 400 ⁇ m) placed on the support table. .5 m / min) to form a laminate.
- the PET film was peeled off, and a pressure-sensitive dicing tape was laminated on the temporary fixing film. Thereafter, the wafer was separated into 3 mm ⁇ 3 mm size chips using a dicer.
- the chip with temporary fixing film thus obtained was thermocompression bonded on a 10 mm ⁇ 10 mm ⁇ 0.40 mm thick silicon substrate with a temporary fixing film on a hot plate at 150 ° C. under conditions of 2000 gf / 10 seconds. did. Then, it heated at 120 degreeC for 1 hour, 180 degreeC for 1 hour, and 260 degreeC for 10 minutes.
- an external force in the shearing direction was applied to the tip side on a 25 ° C. hot plate using a Dage adhesion tester Dage-4000 at a measurement speed of 50 ⁇ m / second and a measurement height of 50 ⁇ m.
- the adhesive strength when added was measured and this was taken as the shear adhesive strength at 25 ° C.
- a having a shear adhesive force at 25 ° C. of 1 MPa or more was designated as A and less than 1 MPa was designated as C.
- Solidility test B A temporary fixing film is rolled (temperature: 150 ° C., linear pressure) on the back surface (the surface opposite to the support table) of a 1/4 silicon wafer (1/4 of a 6-inch diameter and a thickness of 400 ⁇ m) placed on the support table. Lamination was performed by pressurizing at 4 kgf / cm and a feed rate of 0.5 m / min. After peeling off the PET film, a sample obtained in the same manner as in the low temperature sticking test was heated on a hot plate at 120 ° C. for 1 hour, 180 ° C. for 1 hour, and 260 ° C. for 10 minutes.
- the sample was put into a glass container filled with a mixed solvent in which n-propyl alcohol and 25% TMAH aqueous solution were mixed in the same volume, and the temporarily fixing film was dissolved using an ultrasonic cleaner.
- the sample in which the temporarily fixing film was dissolved was designated as A, and the sample that was not dissolved was designated as C.
- the peak temperature of tan ⁇ when an acrylic rubber film was measured using a viscoelasticity measuring device was defined as Tg of acrylic rubber. Specifically, after forming a 30 ⁇ m thick film, it is cut into a size of 10 mm ⁇ 25 mm, and stored under conditions of a heating rate of 5 ° C./min, a frequency of 1 Hz, and a measurement temperature of ⁇ 50 to 300 ° C. Tg was calculated by measuring the temperature dependence of the elastic modulus and tan ⁇ .
- HTR-860P-DR3 Acrylic rubber (manufactured by Nagase ChemteX Corporation) having a weight average molecular weight of 800,000 by GPC, 3% by mass of glycidyl methacrylate, and Tg-7 ° C 2PZ-CN: Imidazole-based curing accelerator (manufactured by Shikoku Chemicals Co., Ltd.)
- TA31-209E Silicone-modified alkyd resin (manufactured by Hitachi Chemical Polymer Co., Ltd.)
- SC2050-SEJ Surface-treated silica filler (manufactured by Admatechs)
- the prepared varnish was applied on a 50 ⁇ m-thick polyethylene terephthalate film subjected to a release treatment, and dried by heating at 90 ° C. for 10 minutes and at 120 ° C. for 30 minutes to obtain a film for temporary fixing with a base film.
- the film thickness of the temporary fixing film was 30 ⁇ m.
- Edge trimming processing was performed on the semiconductor wafer before grinding using a full-diode dicer (manufactured by DISCO Corporation, DFD-6361).
- the blade is VT07-SD2000-VC200-100 (52x1A3x40-L) manufactured by DISCO Corporation.
- Blade rotation speed is 20,000 rpm
- feed rate is 3.0 ° / sec
- cutting depth is 0.2 mm
- trim width is 0.5 mm.
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Abstract
Description
H2N-(CH2)3-O-(CH2)4-O-(CH2)3-NH2、
H2N-(CH2)3-O-(CH2)6-O-(CH2)3-NH2、
H2N-(CH2)3-O-(CH2)2-O-(CH2)2-O-(CH2)3-NH2、
H2N-(CH2)3-O-(CH2)2-O-(CH2)2-O-(CH2)2-O-(CH2)3-NH2
等が挙げられる。
撹拌機、温度計、窒素置換装置(窒素流入管)、及び水分受容器付きの還流冷却器を備えたフラスコ内に、ジアミンである、BAPP(商品名、東京化成製、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン)、分子量410.51)を10.26g(0.025mol)及び1,4-ブタンジオール ビス(3-アミノプロピル)エーテル(東京化成製、商品名:B-12、分子量:204.31)5.10g(0.025mol)と、溶媒である、N-メチル-2-ピロリドン(NMP)100gとを仕込み、撹拌してジアミンを溶媒に溶解させた。
撹拌機、温度計、窒素置換装置(窒素流入管)、及び水分受容器付きの還流冷却器を備えたフラスコ内に、ジアミンである、BAPP(東京化成製、商品名:2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン)、分子量410.51)を8.21g(0.02mol)及び長鎖シロキサンジアミン(信越化学製、商品名:KF8010、分子量:960)28.8g(0.03mol)と、溶媒である、N-メチル-2-ピロリドン(NMP)100gとを仕込み、撹拌してジアミンを溶媒に溶解させた。
撹拌機、温度計、窒素置換装置(窒素流入管)、及び水分受容器付きの還流冷却器を備えたフラスコ内に、ジアミンである、B-12(東京化成製、1,4-ブタンジオール ビス(3-アミノプロピル)エーテル、分子量204.31)を2.04g(0.01mol)、1,3-ビス(3-アミノフェノキシ)ベンゼン(東京化成製、APB-N、分子量292.34)10.23g(0.035mol)及び側鎖フェニル基含有長鎖シロキサンジアミン(信越化学製、商品名:X-22-1660B―3、分子量:4400)22g(0.005mol)と、溶媒である、N-メチル-2-ピロリドン(NMP)100gとを仕込み、撹拌してジアミンを溶媒に溶解させた。
撹拌機、温度計、窒素置換装置(窒素流入管)、及び水分受容器付きの還流冷却器を備えたフラスコ内に、ジアミンである、1,3-ビス(3-アミノフェノキシ)ベンゼン(東京化成製、APB-N、分子量292.34)13.15g(0.045mol)及び側鎖フェニル基含有長鎖シロキサンジアミン(信越化学製、商品名:X-22-1660B―3、分子量:4400)22g(0.005mol)と、溶媒である、N-メチル-2-ピロリドン(NMP)100gとを仕込み、撹拌してジアミンを溶媒に溶解させた。
撹拌機、温度計、窒素置換装置(窒素流入管)、及び水分受容器付きの還流冷却器を備えたフラスコ内に、ジアミンである、BAPP(東京化成製、商品名:2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン)、分子量410.51)を20.52g(0.05mol)と、溶媒である、N-メチル-2-ピロリドン(NMP)100gとを仕込み、撹拌してジアミンを溶媒に溶解させた。
[ワニスの調製]
表2~4に示す組成(単位は質量部)に基づいて、各材料をNMP溶媒中に固形分濃度が50質量%になるように溶解混合してフィルムを形成するためのワニスをそれぞれ作製した。
SKダイン1435:アクリル系粘着剤(綜研化学製)
A-DCP:トリシクロデカンジメタノールジアクリレート(新中村化学社製)
A-9300:エトキシ化イソシアヌル酸トリアクリレート(新中村化学社製)
A-DOG:1,10-デカンジオールアクリレート(新中村化学社製)
UA-512:2官能ウレタンアクリレート(新中村化学社製)
YDF-8170:ビスフェノールF型ビスグリシジルエーテル(東都化成社製)
VG-3101:高耐熱3官能エポキシ樹脂(プリンテック社製)
パークミルD:ジクミルパーオキサイド(日油製)
H27:トリメトキシフェニルシラン修飾球状シリカフィラ(CIKナノテック製)
SC2050SEJ:3-グリシドキシプロピルトリエトキシシラン修飾球状シリカフィラ
HD1100Z:フッ素系表面改質材(ダイキン工業製)
FA-200:フッ素系表面改質材(日産化学製)
2PZ-CN:イミダゾール系硬化促進剤(四国化成製)
作製したワニスをセパレータフィルム(PETフィルム)上にナイフコーターを用いて塗布した後、80℃のオーブンで30分間、ついで、120度のオーブンで30分間乾燥させることによって、厚さ30μmの仮固定用フィルムを作製した。
支持台上に載せたシリコンウェハ(6インチ径、厚さ400μm)の裏面(支持台と反対側の面)に、仮固定用フィルムをロール(温度150℃、線圧4kgf/cm、送り速度0.5m/分)で加圧することにより積層した。PETフィルムを剥がし、仮固定用フィルム上に、厚み80μm、幅10mm、長さ40mmのポリイミドフィルム「ユーピレックス」(商品名)を前記と同様の条件でロールにより加圧して積層した。このようにして準備したサンプルについて、レオメータ「ストログラフE-S」(商品名)を用いて、室温で90°ピール試験を行って、仮固定用フィルムとユーピレックスとの間のピール強度を測定した。ピール強度が2N/cm以上のサンプルをA、2N/cm未満のサンプルをCとした。
支持台上に載せたシリコンウェハ(6インチ径、厚さ400μm)の裏面(支持台と反対側の面)に、仮固定用フィルムをロール(温度80℃、線圧4kgf/cm、送り速度0.5m/分)で加圧することにより積層した。PETフィルムを剥がし、仮固定用フィルム上に、感圧型のダイシングテープをラミネートした。その後、ダイサーを用いてウェハを3mm×3mmサイズのチップに個片化した。こうして得られた仮固定用フィルム付きチップを、10mm×10mm×0.40mm厚のシリコン基板上に、仮固定用フィルムを挟んで、150℃の熱盤上で2000gf/10秒の条件で加熱圧着した。その後、120℃で1時間、180℃で1時間、260℃で10分間加熱した。得られたサンプルについて、Dage製接着力試験機Dage-4000を用いて、25℃の熱盤上で、測定速度:50μm/秒、測定高さ:50μmの条件でチップ側にせん断方向の外力を加えたときの接着力を測定し、これを25℃におけるせん断接着力とした。25℃でのせん断接着力が1MPa以上のものをA、1MPa未満のものをCとした。
上記低温貼付性試験と同様にして得られたサンプルを、ホットプレート上で120℃1時間、180℃1時間、260℃10分間加熱した。その後、サンプルを観察し、発泡が見られなかったサンプルをA、発泡が観察されたサンプルをCとした。
支持台上に載せた1/4シリコンウェハ(6インチ径、厚さ400μmの1/4)の裏面(支持台と反対側の面)に、仮固定用フィルムをロール(温度150℃、線圧4kgf/cm、送り速度0.5m/分)で加圧することにより積層した。PETフィルムを剥がしたのち、上記低温貼付性試験と同様にして得られたサンプルを、ホットプレート上で120℃1時間、180℃1時間、260℃10分間加熱した。その後、NMPを満たしたガラス容器にサンプルを入れ、超音波洗浄機を用いて仮固定用フィルムを溶解させた。仮固定用フィルムが溶解したサンプルをA、溶解しなかったサンプルをCとした。
支持台上に載せた1/4シリコンウェハ(6インチ径、厚さ400μmの1/4)の裏面(支持台と反対側の面)に、仮固定用フィルムをロール(温度150℃、線圧4kgf/cm、送り速度0.5m/分)で加圧することにより積層した。PETフィルムを剥がしたのち、上記低温貼付性試験と同様にして得られたサンプルを、ホットプレート上で120℃1時間、180℃1時間、260℃10分間加熱した。その後、n-プロピルアルコール及び25%TMAH水溶液を同体積で混合した混合溶媒を満たしたガラス容器にサンプルを入れ、超音波洗浄機を用いて仮固定用フィルムを溶解させた。仮固定用フィルムが溶解したサンプルをA、溶解しなかったサンプルをCとした。
撹拌機、温度計、窒素置換装置(窒素流入管)、及び水分受容器付きの還流冷却器を備えた500ccのセパラブルフラスコ内に、脱イオン水200g、アクリル酸ブチル40g、アクリル酸エチル28g、グリシジルメタクリレート3g、アクリロニトリル29g、1.8%ポリビニルアルコール水溶液2.04g、ラウリルパーオキサイド0.41g、及びn-オクチルメルカプタン0.07gを配合した。続いて、60分間N2ガスを吹き込んで系内の空気を除去した後、系内温度を65℃に昇温して3時間重合を行った。さらに、90℃に昇温して2時間攪拌を続け重合を完結させた。得られた透明のビーズをろ過により分離し、イオン水で洗浄した後、真空乾燥機で50℃6時間乾燥させ、アクリルゴムP-1を得た。アクリルゴムP-1をGPCで測定したところ、アクリルゴムP-1の重量平均分子量Mwは、ポリスチレン換算で40万であった。また、アクリルゴムP-1のTgは8℃であった。
撹拌機、温度計、窒素置換装置(窒素流入管)、及び水分受容器付きの還流冷却器を備えた500ccのセパラブルフラスコ内に、脱イオン水200g、アクリル酸ブチル36g、アクリル酸エチル18g、グリシジルメタクリレート3g、メタクリル酸メチル43g、1.8%ポリビニルアルコール水溶液2.04g、ラウリルパーオキサイド0.41g、及びn-オクチルメルカプタン0.07gを配合した。続いて、60分間N2ガスを吹き込んで系内の空気を除去した後、系内温度を65℃に昇温して3時間重合を行った。さらに、90℃に昇温して2時間攪拌を続け重合を完結させた。得られた透明のビーズをろ過により分離し、イオン水で洗浄した後、真空乾燥機で50℃6時間乾燥させ、アクリルゴムP-2を得た。アクリルゴムP-2をGPCで測定したところ、アクリルゴムP-2のMwは、ポリスチレン換算でMw50万であった。また、アクリルゴムP-2のTgは12℃であった。
撹拌機、温度計、窒素置換装置(窒素流入管)、及び水分受容器付きの還流冷却器を備えた500ccのセパラブルフラスコ内に、脱イオン水200g、アクリル酸ブチル59g、アクリル酸エチル41g、1.8%ポリビニルアルコール水溶液2.04g、ラウリルパーオキサイド0.41g、及びn-オクチルメルカプタン0.07gを配合した。続いて、60分間N2ガスを吹き込んで系内の空気を除去した後、系内温度を65℃に昇温して3時間重合を行った。さらに、90℃に昇温して2時間攪拌を続け重合を完結させた。得られた透明のビーズをろ過により分離し、イオン水で洗浄した後、真空乾燥機で50℃6時間乾燥させ、アクリルゴムP-3を得た。アクリルゴムP-3をGPCで測定したところ、アクリルゴムP-3のMwは、ポリスチレン換算で40万であった。また、アクリルゴムP-3のTgは-40℃であった。
アクリルゴム、硬化促進剤、剥離処理剤、フィラ及び塗工溶媒を表8に示す配合割合(単位は質量部)で配合し、ワニスF-01~F-07を調製した。
HTR-860P-DR3:GPCによる重量平均分子量80万、グリシジルメタクリレート3質量%、Tg-7℃のアクリルゴム(ナガセケムテックス(株)製)
2PZ-CN:イミダゾール系硬化促進剤(四国化成工業(株)製)
TA31-209E:シリコーン変性アルキド樹脂(日立化成ポリマー(株)製)
SC2050-SEJ:表面処理シリカフィラ(アドマテックス(株)製)
調製したワニスを、離型処理した厚さ50μmのポリエチレンテレフタレートフィルム上に塗布し、90℃10分間、120℃で30分間加熱乾燥して、基材フィルム付き仮固定用フィルムを得た。仮固定用フィルムの膜厚は、30μmであった。
8インチウェハの鏡面側を表にして、ミカサ(株)製スピンコータMS-A200に設置し、ダイキン工業(株)製フッ素型離型剤(オプツール HD-1000Z)をウェハ上に滴下した後、800rpmで10秒間、続いて1200rpmで30秒間スピンコートを行った。その後、ウェハを120℃に設定したホットプレート上に5分間、続いて150℃に設定したホットプレートに5分間静置し、離型処理剤付き支持部材R-1を得た。
8インチウェハの鏡面側を表にして、ミカサ(株)製スピンコータMS-A200に設置し、日立化成ポリマー(株)製シリコーン変性アルキッド樹脂(TA31-209E)100質量部及びパラトルエンスルホン酸10質量部を配合した固形分10質量%のトルエン溶液をウェハ上に滴下した後、800rpmで10秒間、続いて1500rpmで30秒間スピンコートを行った。その後、ウェハを120℃に設定したホットプレート上に5分間、続けて150℃に設定したホットプレート上に5分間静置し、離型処理剤付き支持部材R-2を得た。
8インチウェハを離型処理せずにそのまま支持部材R-3として用いた。
以下で説明する手順で、上記アクリルゴムをワニス又は仮固定用フィルムの状態で上記支持部材と組み合わせ、各種評価を行った。用いたアクリルゴムの種類、アクリルゴムの状態、支持部材の種類、及び評価結果を表9,10に示す。
研削前の半導体ウェハに対して、フルオードダイサ((株)DISCO製、DFD-6361)を用いてエッジトリミング処理を行った。ブレードは(株)DISCO製VT07-SD2000-VC200-100(52x1A3x40-L)を用い、ブレード回転数20,000rpm、送り速度3.0°/sec、切り込み深さ0.2mm、トリム幅0.5mmの条件とした。
基材フィルム付き仮固定用フィルムを、半導体ウェハのエッジトリミングが施された面の直径よりも2mm小さい直径を有する円形状に切り出した。その後、ニチゴーモートン(株)製真空ラミネーターV130を用い、気圧1hPa以下、圧着温度80℃、ラミネート圧力0.5MPa、保持時間60秒でラミネートを行い、仮固定用フィルム付き半導体ウェハを得た。
エッジトリミングが施された半導体ウェハをミカサ(株)製スピンコータMS-A200に設置し、表1に示すワニスをウェハに適量滴下し、600rpmで10秒間、続いて1500rpmで30秒間スピンコートした。その後、半導体ウェハを90℃に設定したオーブンにて10分間、続いて120℃に設定したオーブンで30分間加熱乾燥して仮固定用フィルム付き半導体ウェハを得た。仮固定用フィルムの膜厚は、30μmであった。
ニチゴーモートン(株)製真空ラミネーターV130を用い、気圧1hPa以下、圧着温度100℃ラミネート圧力0.5MPa、保持時間100秒で、離型処理剤付き支持部材と仮固定用フィルム付き半導体ウェハとを圧着した。その後、110℃に設定したオーブン30分間保持した後、170℃に設定したオーブンで1時間保持し、積層サンプルを得た。
フルオートグラインダポリッシャ((株)DISCO社製、DGP-8761)を用いて積層サンプルにおける半導体ウェハ表面を研削した。ホイールには、1軸:GF01-SDC320-BT300-50、2軸:IF-01-1-4/6-B・K09、3軸:DPEG-GA0001をそれぞれ用いた。チャックテーブル回転数を300rpm、ホイール回転数を1軸:3,200rpm、2軸:3,400rpm、3軸:1,400rpmとし、クロスフィード方式で研削を行った。1軸で142μm厚になるまで研削後、2軸で102μm厚になるまで、3軸で100μm厚になるまで研削した。研削終了時点で割れ等が発生しなかったサンプルをA、割れ等が発生したサンプルをBと評価した。
バックグラインド試験において評価がAであった積層サンプルについて、SAMを用いて仮固定用フィルムの状態を確認した。その後、積層サンプルを200℃に設定したオーブンに2時間放置し、さらに260℃に設定したオーブンに20分間放置した。続いて、再度SAMを用いて仮固定用フィルムの状態を確認し、オーブンに放置しても仮固定用フィルムの剥離が生じなかったサンプルをA、剥離が生じたサンプルをBと評価した。
耐熱性試験において評価がAであった積層サンプルについて、離型処理剤付き支持部材と仮固定用フィルムとの間に先端が鋭利な状態のピンセットを差し入れ、外縁に沿ってピンセットを動かした。このとき、半導体ウェハが割れることなく支持部材を剥離できたサンプルをA、剥離できなかったサンプルをBと評価した。
支持部材からの剥離性試験において評価がAであった積層サンプルについて、半導体ウェハに貼付されている仮固定用フィルムの端部をピンセットにて持ち上げた。このとき、半導体ウェハから仮固定用フィルムを剥離できたサンプルをA、剥離できなかったサンプルをBと評価した。
Claims (6)
- 半導体ウェハを個片化して得られる半導体素子を備える半導体装置の製造方法であって、
支持部材と前記半導体ウェハとの間に仮固定用フィルムを配置し、前記支持部材と前記半導体ウェハとを仮固定する仮固定工程と、
前記支持部材に仮固定された前記半導体ウェハにおける前記仮固定用フィルムと反対側の面を研削する研削工程と、
研削された前記半導体ウェハから前記仮固定用フィルムを剥離する半導体ウェハ剥離工程と、を備え、
前記半導体ウェハとして、前記支持部材と対向する面の外周部にエッジトリミングが施された半導体ウェハを用い、
前記仮固定工程において、前記エッジトリミング部分よりも内側に前記仮固定用フィルムを配置することを特徴とする半導体装置の製造方法。 - 前記支持部材から前記仮固定用フィルムを剥離する支持部材剥離工程を更に備え、
前記支持部材として、前記仮固定用フィルムに対向する面の一部又は全部が離型処理された支持部材を用いることを特徴とする請求項1に記載の半導体装置の製造方法。 - フッ素原子を有する表面改質剤、ポリオレフィン系ワックス、シリコーンオイル、反応性基を含有するシリコーンオイル及びシリコーン変性アルキド樹脂からなる群から選ばれる少なくとも一つの離型処理剤によって前記離型処理を行うことを特徴とする請求項2に記載の半導体装置の製造方法。
- 前記仮固定用フィルムとして、エポキシ基を有するアクリレートモノマ又はエポキシ基を有するメタクリレートモノマを含むアクリルモノマを重合して得られ、重量平均分子量が10万以上であり、Tgが-50℃~50℃であるエポキシ基含有(メタ)アクリル共重合体を含んでなる仮固定用フィルムを用いることを特徴とする請求項1~3のいずれか一項に記載の半導体装置の製造方法。
- 前記エポキシ基を有するアクリレートモノマとしてグリシジルアクリレートモノマを用い、前記エポキシ基を有するメタクリレートモノマとしてグリシジルメタクリレートモノマを用いることを特徴とする請求項4に記載の半導体装置の製造方法。
- 前記仮固定用フィルムとして、シリコーン変性アルキド樹脂を含有する仮固定用フィルムを用いることを特徴とする請求項1~5のいずれか一項に記載の半導体装置の製造方法。
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KR20150013771A (ko) | 2015-02-05 |
JPWO2014003056A1 (ja) | 2016-06-02 |
CN104412369A (zh) | 2015-03-11 |
JP6209876B2 (ja) | 2017-10-11 |
TWI587407B (zh) | 2017-06-11 |
TW201411742A (zh) | 2014-03-16 |
JP2014029999A (ja) | 2014-02-13 |
US20150179494A1 (en) | 2015-06-25 |
KR101683705B1 (ko) | 2016-12-07 |
JP5962759B2 (ja) | 2016-08-03 |
CN104412369B (zh) | 2017-05-24 |
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