WO2019098334A1 - Semiconductor chip with first protective film, method for manufacturing semiconductor chip with first protective film, and method for evaluating laminate of semiconductor chip and first protective film - Google Patents

Semiconductor chip with first protective film, method for manufacturing semiconductor chip with first protective film, and method for evaluating laminate of semiconductor chip and first protective film Download PDF

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Publication number
WO2019098334A1
WO2019098334A1 PCT/JP2018/042521 JP2018042521W WO2019098334A1 WO 2019098334 A1 WO2019098334 A1 WO 2019098334A1 JP 2018042521 W JP2018042521 W JP 2018042521W WO 2019098334 A1 WO2019098334 A1 WO 2019098334A1
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Prior art keywords
protective film
semiconductor chip
bump
residue
bumps
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PCT/JP2018/042521
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French (fr)
Japanese (ja)
Inventor
圭亮 四宮
明徳 佐藤
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リンテック株式会社
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Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to KR1020207013182A priority Critical patent/KR102616422B1/en
Priority to CN201880072999.7A priority patent/CN111357088A/en
Priority to JP2019554317A priority patent/JP7218297B2/en
Publication of WO2019098334A1 publication Critical patent/WO2019098334A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—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 at least one potential-jump barrier or surface barrier, e.g. 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
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/2209—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using wavelength dispersive spectroscopy [WDS]
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L22/00—Testing or measuring during manufacture or treatment; Reliability measurements, i.e. testing of parts without further processing to modify the parts as such; Structural arrangements therefor
    • H01L22/10—Measuring as part of the manufacturing process
    • H01L22/12—Measuring as part of the manufacturing process for structural parameters, e.g. thickness, line width, refractive index, temperature, warp, bond strength, defects, optical inspection, electrical measurement of structural dimensions, metallurgic measurement of diffusions
    • 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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/11—Manufacturing methods

Definitions

  • the present invention relates to a semiconductor chip with a first protective film, a method of manufacturing a semiconductor chip with a first protective film, and a method of evaluating a semiconductor chip / first protective film laminate.
  • a convex electrode (hereinafter referred to as a semiconductor chip) made of eutectic solder, high temperature solder, gold etc.
  • a semiconductor chip made of eutectic solder, high temperature solder, gold etc.
  • these bumps are made to face and contact corresponding terminal portions on the chip mounting substrate by the so-called face-down method, and melting / diffusion A flip chip mounting method to bond has been employed.
  • the semiconductor chip used in this mounting method is, for example, a semiconductor wafer having bumps formed on the circuit surface, and the surface on the opposite side to the circuit surface (in other words, the bump formation surface) is ground or the semiconductor wafer is diced. It is obtained by fragmenting.
  • a curable resin film is attached to the bump formed surface, and this film is cured to form the bump formed surface. Form a protective film.
  • the curable resin film is usually attached to the bump formation surface of the semiconductor wafer in a softened state by heating. By doing this, the upper portion including the top of the bump penetrates the curable resin film and protrudes from the curable resin film.
  • the curable resin film spreads between the bumps so as to cover the bumps of the semiconductor wafer and adheres to the bump formation surface, and covers the surface of the bumps, particularly the surface near the bump formation surface.
  • the curable resin film is further cured to cover the bump formation surface of the semiconductor wafer and the surface of the vicinity of the bump formation surface of the bump, to form a protective film for protecting these regions.
  • the semiconductor wafer is singulated into semiconductor chips, and finally, a semiconductor chip provided with a protective film on the bump formation surface (sometimes referred to as “semiconductor chip with protective film” in the present specification) Become.
  • Such a semiconductor chip with a protective film is mounted on a substrate to be a semiconductor package, and the semiconductor package is used to form a target semiconductor device.
  • the semiconductor package and the semiconductor device it is necessary that the electrical connection between the bump of the semiconductor chip with a protective film and the circuit on the substrate is not inhibited.
  • the curable resin film is not appropriately attached to the bump formation surface of the semiconductor wafer, the protrusion of the bump from the curable resin film may be insufficient, or the curable resin film may be formed on the top of the bump. Some will survive.
  • the curable resin film remaining on the top of the bumps is cured as in the case of the curable resin film in the other regions, and a cured product having a composition similar to that of the protective film (herein, It may be called "protective film residue".
  • a cured product having a composition similar to that of the protective film herein, It may be called "protective film residue”.
  • the top of the bump is an electrical connection area between the bump and the circuit on the substrate, the bump on the semiconductor chip with the protective film, and the circuit on the substrate, when the amount of protective film residue is large. , The electrical connection of will be blocked. That is, at the stage before mounting the semiconductor chip with a protective film on the substrate, at the top of the bump of the semiconductor chip with a protective film, there is no protective film residue or the amount of protective film residue is small. Is required.
  • Patent Document 1 discloses a method of using a curable resin film (adhesive / adhesive layer) containing an agent, a photoreactive monomer, and a photoinitiator.
  • the present invention relates to a semiconductor chip with a protective film in which the remaining of a protective film residue is suppressed at the top of the bump, a method of manufacturing the semiconductor chip with a protective film, and whether it is the semiconductor chip with a protective film. It aims at providing an evaluation method that can be evaluated with high accuracy.
  • the present invention comprises a semiconductor chip and a first protective film formed on the surface of the semiconductor chip having a bump, and the top of the bump is analyzed by energy dispersive X-ray spectroscopy to obtain carbon
  • the present invention is a method for producing the semiconductor chip with a first protective film, which comprises the steps of attaching a curable resin film to the surface of the semiconductor wafer having bumps, and curing the curable resin film after attachment. Forming a first protective film, and dividing the semiconductor wafer to obtain a semiconductor chip, and attaching the curable resin film, wherein the S (C) is formed.
  • a method of manufacturing a semiconductor chip with a first protective film comprising the step of reducing the amount of residue on the bumps such that the value of S (C) / S (Sn) is 0.32 or less.
  • a method of evaluating a semiconductor chip / first protective film laminate comprising: a semiconductor chip; and a first protective film formed on a surface of the semiconductor chip having a bump.
  • the top of the bump in the chip / first protective film stack is analyzed by energy dispersive X-ray spectroscopy, and the intensity S (C) of the carbon detection signal and the intensity S (Sn) of the detection signal of tin ), And when the value of S (C) / S (Sn) is 0.32 or less, the semiconductor chip / first protective film laminate is a target semiconductor with a first protective film When it is determined that the chip is a chip, and the value of S (C) / S (Sn) is larger than 0.32, the semiconductor chip / first protective film laminate is used as a target semiconductor with a first protective film Semiconductor chip, first protective film that is judged not to be a chip It provides a method for evaluating lamina.
  • the residual of the protective film residue is suppressed at the top of the bump.
  • a bonded body having a high degree of electrical connection can be obtained.
  • the method for manufacturing a semiconductor chip with a first protective film of the present invention the above-described semiconductor chip with a first protective film can be manufactured.
  • the evaluation method of the semiconductor chip / first protective film laminate of the present invention it is possible to accurately determine whether the semiconductor chip / first protective film laminate is the above-described semiconductor chip with a first protective film. It can be evaluated.
  • FIG. 7 is an enlarged cross sectional view for schematically illustrating another example of the step of reducing the amount of residue on bumps in the method of manufacturing a semiconductor chip with a first protective film of the present invention.
  • FIG. 14 is an enlarged cross sectional view for schematically illustrating still another example of the step of reducing the amount of residue on bumps in the method of manufacturing a semiconductor chip with a first protective film of the present invention.
  • FIG. 14 is an enlarged cross sectional view for schematically illustrating still another example of the step of reducing the amount of residue on bumps in the method of manufacturing a semiconductor chip with a first protective film of the present invention.
  • it is a top view for explaining the arrangement position on a dicing tape of the semiconductor chip and the 1st protective film layered product which is the object which performs EDX analysis about the top of a bump.
  • the semiconductor chip with a first protective film of the present invention is a semiconductor chip, and a surface having bumps of the semiconductor chip (sometimes referred to as a “bump forming surface” in the present specification)
  • a first protective film formed on the top of the bump, and the top of the bump may be referred to as "energy dispersive X-ray spectrometry (EDX)" in the present specification.
  • EDX energy dispersive X-ray spectrometry
  • the tin (Sn) signal is detected because the bump contains tin as its constituent material.
  • the bump does not contain an organic compound as its constituent material. Therefore, when the top of the bump is analyzed by EDX, the carbon (C) signal is detected because there is an organic compound which is not originally present in the analysis area (that is, the top of the bump). It is. This organic compound originates in the curable resin film used at the time of formation of the first protective film.
  • curable resin film residue As it cures, it sometimes becomes a cured product having the same composition as the first protective film (sometimes referred to herein as “first protective film residue”).
  • the first protective film residue contains the organic compound described above.
  • a signal of carbon (C) is detected when the top of the bump is analyzed by EDX. The method of manufacturing the semiconductor chip with a first protective film of the present invention will be described in detail later.
  • the S (C) / S (Sn) value at the top of the bump is 0.32 or less, and may be zero. This means that the amount of carbon is significantly lower than the amount of tin at the top of the bump. That is, in the semiconductor chip with the first protective film, the first protective film residue does not exist or the amount of the first protective film residue is small at the top of the bump, and the residual of the first protective film residue is suppressed It is done. Thus, when the semiconductor chip with the first protective film is used by suppressing the remaining of the first protective film residue at the top of the bump, the bonding strength between the bump and the substrate is obtained. Becomes higher. In addition, the degree of electrical connection in the joined body of the semiconductor chip and the substrate is high, and the conductivity is excellent.
  • the amount of the first protective film residue is small at the top of the bump means that the first protective film remains slightly at the top of the bump unless otherwise specified. However, this means that the remaining amount is such that it does not prevent the electrical connection between the semiconductor chip and the wiring substrate when the semiconductor chip having the bumps is flip-chip mounted on the wiring substrate. Moreover, the surface on the opposite side to the bump formation surface of a semiconductor wafer may be called a "back surface.”
  • the first protection is in the concave portion of the bump surface. It is possible that membrane residue has penetrated.
  • the first protective film residue in such a recess is difficult to confirm and quantify by visual methods, and is particularly strong when the amount of the first protective film residue is small.
  • the semiconductor chip with a first protective film of the present invention the degree of remaining of the first protective film residue at the top of the bump is precisely specified based on the analysis result by EDX. Therefore, the semiconductor chip with a first protective film of the present invention is extremely reliable in terms of the amount of the first protective film residue.
  • the S (C) / S (Sn) value at the top of the bump is 0.32 or less, preferably 0.3 or less, and 0.28 or less Is more preferably 0.26 or less, and may be 0.2 or less, 0.15 or less, or 0.1 or less, for example.
  • the S (C) / S (Sn) value is less than or equal to the upper limit value, the residual of the first protective film residue is further suppressed at the top of the bump, so that the semiconductor chip with the first protective film The effect of the present invention to play is more remarkable.
  • the lower limit value of the S (C) / S (Sn) value at the top of the bump is not particularly limited as long as it is 0 or more.
  • the S (C) / S (Sn) value may be 0.03 or more, and such a semiconductor chip with a first protective film can be manufactured more easily.
  • the S (C) / S (Sn) value at the top of the bump is within the range set by any combination of the lower limit and the upper limit described above. , Can be adjusted accordingly.
  • the S (C) / S (Sn) value is preferably 0 to 0.32, more preferably 0 to 0.3, still more preferably 0 to 0.28, particularly preferably 0 to It may be 0.26, for example, any of 0 to 0.2, 0 to 0.15, and 0 to 0.1 or the like.
  • the S (C) / S (Sn) value is preferably 0.03 to 0.32, more preferably 0.03 to 0.3, and still more preferably 0.03 to 0.28. And particularly preferably 0.03 to 0.26, and may be, for example, 0.03 to 0.2, 0.03 to 0.15, and 0.03 to 0.1 or the like.
  • the top of the bump where EDX analysis is performed means the upper area including the top of the bump.
  • the top of the head includes, for example, the top of the bump when the bump is viewed from above and viewed from above, and the diameter is preferably 80 to 120 ⁇ m, more preferably 90 to 110 ⁇ m, for example 100 ⁇ m An area recognized as a circular area may be mentioned. Such a region is a scanning range in EDX. When the diameter is equal to or more than the lower limit value, EDX analysis can be performed with higher accuracy. When the diameter is equal to or less than the upper limit value, EDX analysis can be performed with higher efficiency.
  • the highest position from the bump formation surface of the semiconductor chip can be selected as the top of the bump.
  • the surface of the upper region of the bump is a plane, for example, the center (center of gravity) of the plane can be selected as the top of the bump.
  • the shape of the bumps will be described in detail later.
  • the analysis conditions in EDX are not particularly limited. However, usually, the acceleration voltage is preferably 15 to 30 kV, and the distance between the lens and the sample is preferably 10 to 15 mm. Under such conditions, analysis can be performed with higher accuracy.
  • FIG. 1 is an enlarged cross-sectional view schematically showing an embodiment of a semiconductor chip with a first protective film of the present invention. Note that the drawings used in the following description may be enlarged for convenience, in order to make the features of the present invention intelligible. Not necessarily.
  • the semiconductor chip 1 with a first protective film shown here includes a semiconductor chip 9 and a first protective film 13 formed on a surface (bump formation surface) 9 a having bumps of the semiconductor chip 9.
  • the first protective film 13 is in close contact with the bump forming surface 9a and covers the surface 91a of the bump 91, particularly the surface 91a in the vicinity of the bump forming surface 9a. Embed and protect these areas.
  • reference numeral 9 b denotes a surface (rear surface) opposite to the bump forming surface 9 a of the semiconductor chip 9.
  • the top portions 910 of the bumps 91 protrude through the first protective film 13. Furthermore, the top portion 910 of the bump 91 is free of the first protective film residue. Therefore, when EDX analysis is performed on the top of the bumps 91 of the bumps 91, the S (C) / S (Sn) value becomes as low as 0.32 or less.
  • the bump 91 has a shape in which a part of the sphere is cut off by a plane, and the plane corresponding to the cut and exposed portion is in contact with the bump forming surface (circuit surface) 9 a of the semiconductor chip 9 It has become.
  • the shape of the bumps 91 can be said to be generally spherical.
  • the top portion 910 of the bump 91 is a curved surface although it is part of a spherical surface.
  • the height of the bumps 91 is not particularly limited, but is preferably 60 to 450 ⁇ m, more preferably 120 to 300 ⁇ m, and particularly preferably 180 to 240 ⁇ m.
  • the function of the bump 91 can be further improved.
  • the height of the bumps 91 is equal to or less than the upper limit value, the effect of suppressing the remaining of the first protective film residue in the top portion 910 of the bumps 91 becomes higher.
  • the height of the bump means the height at the portion (the top) of the bump which is at the highest position from the bump formation surface.
  • the width of the bumps 91 is not particularly limited, but is preferably 170 to 350 ⁇ m, more preferably 200 to 320 ⁇ m, and particularly preferably 230 to 290 ⁇ m.
  • the width of the bump 91 is equal to or more than the lower limit value, the function of the bump 91 can be further improved.
  • the width of the bump 91 is equal to or less than the upper limit value, the effect of suppressing the remaining of the first protective film residue in the top portion 910 of the bump 91 is further enhanced.
  • the “bump width” can be obtained by connecting two different points on the surface of the bump with a straight line when the bump is viewed from below in a direction perpendicular to the surface on which the bump is formed. It means the maximum value of the line segment.
  • the distance between adjacent bumps 91 is not particularly limited, but is preferably 80 to 1000 ⁇ m, more preferably 100 to 800 ⁇ m, and particularly preferably 120 to 550 ⁇ m.
  • the function of the bump 91 can be further improved by the distance being equal to or more than the lower limit value.
  • the distance between adjacent bumps means the distance between the central portions of adjacent bumps, and may be referred to as "bump pitch”.
  • the semiconductor chip with a first protective film is shown for the one in which the first protective film residue is not present on the top of the bump, the semiconductor chip with a first protective film of the present invention is the top of the bump.
  • a small amount of the first protective film residue may be present. The amount of the first protective film residue at this time may be small as described above.
  • FIG. 2 is an enlarged sectional view schematically showing an embodiment of such a semiconductor chip with a first protective film of the present invention.
  • the semiconductor chip with a first protective film 2 shown here is the semiconductor chip with a first protective film 1 shown in FIG. 1 except that a small amount of the first protective film residue 131 is present on the top portion 910 of the bump 91. Is the same as
  • the top portion 910 of the bump 91 penetrates the first protective film 13 and protrudes.
  • the amount of the first protective film residue 131 is small at the top portion 910 of the bump 91, and the residual of the first protective film residue 131 is suppressed. Therefore, when EDX analysis is performed on the top of the bumps 91 of the bumps 91, the S (C) / S (Sn) value becomes as low as 0.32 or less.
  • the first protective film residue 131 is present in a narrow region of the surface 91 a of the bump 91, with the top of the top portion 910 of the bump 91 substantially centered on the top.
  • the case is shown.
  • the region where the first protective film residue 131 is present is not limited to this, and may not be centered on the top of the bump 91 or in the vicinity thereof, for example.
  • “the top of the bump (the top in the top of the bump)” means a portion of the surface of the bump that is the highest in height from the surface on which the semiconductor chip is formed.
  • the shape of the bumps is not limited thereto.
  • FIG. 3 is an enlarged cross-sectional view schematically showing an embodiment of the semiconductor chip with a first protective film of the present invention in which the shape of the bumps is not approximately spherical.
  • the semiconductor chip 3 with a first protective film shown here is the same as the semiconductor chip 1 with a first protective film shown in FIG. 1 except that the semiconductor chip 3 with the first protective film is provided with bumps 92 instead of the bumps 91 (that is, the shapes of the bumps are different). is there. More specifically, in the bumps 91 shown in FIG. 1, the bumps 92 are such that the tops 910 are not curved but flat. That is, the tops 920 of the bumps 92 are flat.
  • reference numeral 92 a indicates the surface of the area of the bump 92 other than the crown portion 920.
  • the surface of the top portion 920 of the bump 92 may or may not be parallel to the bump formation surface 9 a of the semiconductor chip 9. And if not parallel, the orientation of the surface of the crown 920 is not particularly limited.
  • Top portions 920 of the bumps 92 protrude through the first protective film 13. Furthermore, the top portion 920 of the bump 92 is free of the first protective film residue. Therefore, when EDX analysis is performed on the top of the head portion 920 of the bump 92, the S (C) / S (Sn) value becomes as low as 0.32 or less.
  • the width of the bumps 92 and the distance between the adjacent bumps 92 are the same as in the case of the bumps 91 shown in FIG.
  • the height of the bumps 92 is not particularly limited, but is preferably 40 to 390 ⁇ m, more preferably 70 to 250 ⁇ m, and particularly preferably 130 to 190 ⁇ m.
  • the function of the bump 92 can be further improved.
  • the height of the bumps 92 is equal to or less than the upper limit value, the effect of suppressing the remaining of the first protective film residue in the top portion 920 of the bumps 92 becomes higher.
  • the semiconductor chip with a first protective film is shown for the one in which the first protective film residue is not present on the top of the bump, the semiconductor chip with a first protective film of the present invention is the top of the bump.
  • a small amount of the first protective film residue may be present. The amount of the first protective film residue at this time may be small as described above.
  • FIG. 4 is an enlarged sectional view schematically showing an embodiment in the case where a small amount of the first protective film residue is present at the top of the bump in the semiconductor chip with the first protective film of the present invention.
  • the semiconductor chip 4 with a first protective film shown here is the semiconductor chip 3 with a first protective film shown in FIG. 3 except that a small amount of the first protective film residue 131 is present on the top portion 920 of the bump 92. Is the same as
  • the top portion 920 of the bump 92 penetrates the first protective film 13 and protrudes.
  • the amount of the first protective film residue 131 is small at the top portion 920 of the bump 92, and the remaining of the first protective film residue 131 is suppressed. Therefore, when EDX analysis is performed on the top of the head portion 920 of the bump 92, the S (C) / S (Sn) value becomes as low as 0.32 or less.
  • the present region in the case where the first protective film residue 131 is present is not limited to this, and for example, it may not be present from the approximate center of the bump 92 to the surrounding region.
  • the semiconductor chip with a first protective film of the present invention is not limited to those shown in FIGS. 1 to 4 and, for example, some of the semiconductor chips shown in FIGS. 1 to 4 can be used as long as the effects of the present invention are not impaired.
  • the configuration of may be changed, deleted or added.
  • the semiconductor chip with a first protective film shown in FIGS. 1 to 4 has nothing on the back surface 9 b of the semiconductor chip 9 and the back surface 9 b is an exposed surface.
  • the semiconductor chip with a film may be provided with any layer (film) such as a protective film (sometimes referred to as a “second protective film” in the present specification) on the back surface of the semiconductor wafer.
  • the second protective film is a crack in the semiconductor chip when the semiconductor wafer is diced to produce the above-described semiconductor chip, or while the semiconductor chip obtained by the dicing is packaged to manufacture a semiconductor device.
  • the second protective film is usually a resin film.
  • the semiconductor chip is not particularly limited as long as it has bumps on a bump formation surface (a surface provided with a circuit or also referred to as a circuit surface) and can be used for flip chip mounting.
  • examples of the metal that the bump contains as its constituent material include tin (Sn), and as the other metals, for example, gold (Au), silver (Ag), copper (Cu) Etc.
  • the constituent material of the bumps may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the shape, size, and arrangement of the bumps are as described above.
  • the constituent materials and sizes of the portions of the semiconductor chip excluding the bumps may be the same as known ones.
  • the thickness of the portion of the semiconductor chip excluding the bumps is preferably 50 to 780 ⁇ m, and more preferably 150 to 400 ⁇ m.
  • the first protective film adheres to the bump forming surface of the semiconductor chip and covers the surface of the bump, particularly the surface near the bump forming surface of the semiconductor chip to embed the bump. There is. As described above, the first protective film covers the bump formation surface and the surface of the vicinity of the bump formation surface of the bump in the semiconductor chip to protect these regions. There may be a void part between the surface of the vicinity of the bump formation surface of the bump and the first protective film.
  • the first protective film is usually a resin film containing a resin component, and can be formed using a curable resin film for forming the first protective film by curing.
  • a curable resin film can be formed using the composition for curable resin film formation containing the constituent material.
  • the curable resin film-forming composition can be applied to the formation target surface of the curable resin film, and dried as needed, to form a curable resin film at a target location.
  • the ratio of the contents of the components which do not vaporize at normal temperature in the composition for forming a curable resin film is usually the same as the ratio of the contents of the components of the curable resin film.
  • normal temperature means a temperature which is not particularly cooled or heated, ie, a normal temperature, and includes, for example, a temperature of 15 to 25 ° C. and the like.
  • the components corresponding to the resin in the composition for forming a thermosetting resin film and the composition for forming an energy ray-curable resin film described later are all included in the resin component.
  • the first protective film can be formed by curing the curable resin film after forming the curable resin film using the curable resin film-forming composition.
  • the coating of the curable resin film-forming composition may be performed by a known method.
  • the coating method include various coaters such as an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, kiss coater, etc.
  • various coaters such as an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, kiss coater, etc.
  • the drying conditions of the composition for forming a curable resin film are not particularly limited, and it is preferable to appropriately adjust so that the curable component in the composition does not cause curing other than the purpose.
  • the composition for curable resin film formation contains the solvent mentioned later, it is preferable to make it heat-dry.
  • the composition for forming a curable resin film containing a solvent is preferably dried, for example, at 70 to 130 ° C. for 10 seconds to 5 minutes.
  • the first protective film may be only one layer (single layer) or may be a plurality of layers of two or more layers, and in the case of a plurality of layers, the plurality of layers may be the same or different from each other, and a combination of these layers Is not particularly limited.
  • a plurality of layers may be the same as or different from each other” means “all layers may be the same or all layers. May mean that only some of the layers may be the same, and further, “a plurality of layers are different from each other” means “at least one of the constituent material and thickness of each layer is different from each other” "Means.
  • the thickness of the first protective film is preferably 1 to 100 ⁇ m, more preferably 5 to 75 ⁇ m, and particularly preferably 5 to 50 ⁇ m.
  • the thickness of the first protective film is not less than the lower limit value, the protective ability of the first protective film becomes higher.
  • the thickness of the first protective film is equal to or less than the upper limit value, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
  • the thickness of the first protective film means the thickness of the entire first protective film, and for example, the thickness of the first protective film composed of a plurality of layers means all of the components of the first protective film. Means the total thickness of the layers.
  • the first protective film may be either a cured product of a thermosetting resin film or a cured product of an energy ray curable resin film. That is, the first protective film may be formed using any of the thermosetting resin film forming composition and the energy ray curable resin film forming composition.
  • the term "energy beam” means one having an energy quantum among electromagnetic waves or charged particle beams, and examples thereof include ultraviolet rays, radiation, electron beams and the like.
  • the ultraviolet light can be irradiated, for example, by using a high pressure mercury lamp, a fusion lamp, a xenon lamp, a black light or an LED lamp as an ultraviolet light source.
  • the electron beam can irradiate what was generated by the electron beam accelerator or the like.
  • “energy ray curing property” means the property of curing by irradiation with energy rays
  • non energy ray curing property means the property of not curing even by irradiation of energy rays. .
  • composition for forming thermosetting resin film for example, a composition for forming a thermosetting resin film (III) containing a polymer component (A) and a thermosetting component (B) (in the present specification, There may be mentioned simply as "the composition for forming a resin layer (III)" and the like.
  • the polymer component (A) is a polymer compound for imparting film forming property, flexibility and the like to a thermosetting resin film, and is a component which can be regarded as formed by polymerization reaction of a polymerizable compound. In the present specification, the polymerization reaction also includes a polycondensation reaction.
  • the polymer component (A) contained in the resin layer-forming composition (III) and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination thereof and The ratio can be selected arbitrarily.
  • polymer component (A) polyvinyl acetal, acrylic resin (resin which has a (meth) acryloyl group) etc. are mentioned, for example.
  • (meth) acryloyl group is a concept including both “acryloyl group” and “methacryloyl group”.
  • (meth) acrylic acid is a concept including both “acrylic acid” and “methacrylic acid”, “(meth) acrylic acid”.
  • (acrylate” is a concept encompassing both "acrylate” and "methacrylate”.
  • polyvinyl acetal in a polymer component (A) a well-known thing is mentioned.
  • preferable polyvinyl acetals include, for example, polyvinyl formal, polyvinyl butyral and the like, and polyvinyl butyral is more preferable.
  • polyvinyl butyral those having structural units represented by the following formulas (i) -1, (i) -2 and (i) -3 can be mentioned.
  • the weight average molecular weight (Mw) of the polyvinyl acetal is preferably 100,000 or less, more preferably 70,000 or less, and particularly preferably 40,000 or less. When the weight average molecular weight of the polyvinyl acetal is in such a range, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
  • the lower limit value of the weight average molecular weight of the polyvinyl acetal is not particularly limited. However, in terms of further improving the strength and heat resistance of the first protective film, the weight average molecular weight of the polyvinyl acetal is preferably 5000 or more, and more preferably 8000 or more.
  • the weight average molecular weight of the polyvinyl acetal can be appropriately adjusted so as to fall within the range set by arbitrarily combining any of the lower limit value and the upper limit value described above.
  • the weight average molecular weight of the polyvinyl acetal is preferably 5,000 to 100,000, more preferably 5,000 to 70000, and particularly preferably 5,000 to 40,000.
  • the weight average molecular weight of the polyvinyl acetal is preferably 8,000 to 100,000, more preferably 8,000 to 70,000, and particularly preferably 8,000 to 40,000.
  • the glass transition temperature (Tg) of the polyvinyl acetal is preferably 40 to 80 ° C., and more preferably 50 to 70 ° C. When the Tg of the polyvinyl acetal is in such a range, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
  • the ratio of three or more types of monomers constituting the polyvinyl acetal can be arbitrarily selected.
  • acrylic resin in the polymer component (A) examples include known acrylic polymers.
  • the weight average molecular weight (Mw) of the acrylic resin is preferably 300000 or less, more preferably 150,000 or less, and particularly preferably 100,000 or less. When the weight average molecular weight of the acrylic resin is in such a range, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
  • the lower limit value of the weight average molecular weight of the acrylic resin is not particularly limited. However, from the viewpoint of further improving the strength and heat resistance of the first protective film, the weight average molecular weight of the acrylic resin is preferably 10000 or more, and more preferably 30000 or more.
  • the weight average molecular weight of the acrylic resin can be appropriately adjusted so as to fall within a range set by arbitrarily combining any of the lower limit value and the upper limit value described above.
  • the weight average molecular weight of the acrylic resin is preferably 10,000 to 300,000, more preferably 10,000 to 150,000, and particularly preferably 10,000 to 100,000.
  • the weight average molecular weight of the acrylic resin is preferably 30,000 to 300,000, more preferably 30,000 to 150,000, and particularly preferably 30,000 to 100,000.
  • the glass transition temperature (Tg) of the acrylic resin is preferably ⁇ 50 to 70 ° C., and more preferably ⁇ 30 to 60 ° C.
  • Tg of the acrylic resin is in such a range, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
  • the monomer constituting the acrylic resin may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the acrylic resin for example, a polymer of one or more kinds of (meth) acrylic acid esters; (Meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and copolymers of two or more monomers selected from N-methylol acrylamide and the like; 1 type or 2 or more types of (meth) acrylic acid ester, 1 type or 2 or more types of monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylol acrylamide and the like, And the like.
  • Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic Heptyl acid, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , (Meth) acrylic acid undecyl
  • the acrylic resin may have a functional group capable of binding to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group and an isocyanate group.
  • the functional group of the acrylic resin may be bonded to another compound through a crosslinking agent (F) described later, or may be directly bonded to another compound without the crosslinking agent (F) .
  • F crosslinking agent
  • the ratio of the content of the polymer component (A) to the total content of all the components other than the solvent that is, the content of the polymer component (A) of the thermosetting resin film
  • the amount of (5) is preferably 5 to 25% by mass, and more preferably 5 to 15% by mass, regardless of the type of the polymer component (A).
  • thermosetting component (B) is a component for curing the thermosetting resin film using heat as a trigger for the reaction to form a hard first protective film.
  • the thermosetting component (B) contained in the resin layer-forming composition (III) and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination thereof And the ratio can be selected arbitrarily.
  • thermosetting component (B) is preferably an epoxy-based thermosetting resin.
  • the epoxy-based thermosetting resin comprises an epoxy resin (B1) and a thermosetting agent (B2).
  • the epoxy-based thermosetting resin contained in the composition (III) for forming a resin layer and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination thereof and The ratio can be selected arbitrarily.
  • Epoxy resin (B1) As an epoxy resin (B1), a well-known thing is mentioned, for example, a polyfunctional epoxy resin, a biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated substance, an ortho cresol novolak epoxy resin, a dicyclopentadiene type epoxy resin, The bifunctional or more epoxy compound such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. may be mentioned.
  • the epoxy resin (B1) may be an epoxy resin having an unsaturated hydrocarbon group.
  • An epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained using the first protective film containing an epoxy resin having an unsaturated hydrocarbon group and an acrylic resin is improved.
  • an epoxy resin which has an unsaturated hydrocarbon group the compound formed by converting a part of epoxy group of polyfunctional epoxy resin into the group which has an unsaturated hydrocarbon group is mentioned, for example.
  • a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group.
  • an epoxy resin which has an unsaturated hydrocarbon group the compound etc. which the group which has an unsaturated hydrocarbon group directly couple
  • the unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth) acryloyl group, (meth) An acrylamide group etc. are mentioned and an acryloyl group is preferable.
  • the weight average molecular weight of the epoxy resin (B1) is preferably 30,000 or less, more preferably 20,000 or less, and particularly preferably 10,000 or less. When the weight average molecular weight of the epoxy resin (B1) is less than or equal to the upper limit value, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
  • the lower limit value of the weight average molecular weight of the epoxy resin (B1) is not particularly limited.
  • the weight average molecular weight of the epoxy resin (B1) is preferably 300 or more, and preferably 500 or more, in that the curability of the thermosetting resin film and the strength and heat resistance of the first protective film are further improved. It is more preferable that
  • the weight average molecular weight of the epoxy resin (B1) can be appropriately adjusted so as to fall within the range set by arbitrarily combining any of the lower limit value and the upper limit value described above.
  • the weight average molecular weight of the epoxy resin (B1) is preferably 300 to 30,000, more preferably 300 to 20,000, and particularly preferably 300 to 10,000.
  • the weight average molecular weight of the epoxy resin (B1) is preferably 500 to 30,000, more preferably 500 to 20,000, and particularly preferably 500 to 10,000.
  • the epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000 g / eq, and more preferably 300 to 800 g / eq.
  • the epoxy resin (B1) is preferably one that is liquid at normal temperature (sometimes referred to herein simply as "liquid epoxy resin (B1)"). By using such an epoxy resin (B1), the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
  • An epoxy resin (B1) may be used individually by 1 type, and 2 or more types may be used together, and when using 2 or more types together, the combination and ratio of those can be selected arbitrarily.
  • the proportion of the liquid epoxy resin (B1) in the epoxy resin (B1) contained in the resin layer-forming composition (III) and the thermosetting resin film is preferably 40% by mass or more, and 50% by mass % Or more, more preferably 55% by mass or more, for example, 60% by mass or more, 70% by mass or more, 80% by mass or more, and 90% by mass or more.
  • the ratio is equal to or more than the lower limit value, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
  • the upper limit of the ratio is not particularly limited, and the ratio may be 100% by mass or less.
  • thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
  • a thermosetting agent (B2) the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example.
  • the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, and a group in which an acid group is anhydrated, and the phenolic hydroxyl group, an amino group, or an acid group is anhydrated. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.
  • thermosetting agents (B2) as a phenol-based curing agent having a phenolic hydroxyl group, for example, polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-based phenol resins, aralkylphenol resins and the like can be mentioned.
  • the amine-based curing agent having an amino group among the heat curing agents (B2) include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).
  • the thermosetting agent (B2) may have an unsaturated hydrocarbon group.
  • the thermosetting agent (B2) having an unsaturated hydrocarbon group for example, a compound obtained by substituting a part of hydroxyl groups of a phenol resin with a group having an unsaturated hydrocarbon group, an aromatic ring of a phenol resin, The compound etc. which a group which has a saturated hydrocarbon group directly couple
  • bonds are mentioned.
  • the said unsaturated hydrocarbon group in a thermosetting agent (B2) is a thing similar to the unsaturated hydrocarbon group in the epoxy resin which has the above-mentioned unsaturated hydrocarbon group.
  • thermosetting agents (B2) for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, aralkyl phenol resin and the like is preferably 300 to 30000, It is more preferably 400 to 10,000, and particularly preferably 500 to 5,000.
  • the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.
  • thermosetting agent (B2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and a ratio can be selected arbitrarily.
  • the content of the thermosetting agent (B2) is 0.1 to 500 parts by mass with respect to 100 parts by mass of the epoxy resin (B1). Is preferably 1 to 200 parts by mass, and more preferably 1 to 150 parts by mass, 1 to 100 parts by mass, 1 to 75 parts by mass, 1 to 50 parts by mass, and 1 to 30 parts by mass. It may be any of the above.
  • the content of the thermosetting agent (B2) is equal to or more than the lower limit value, curing of the thermosetting resin film becomes easier to progress.
  • the content of the thermosetting agent (B2) is not more than the upper limit value, the moisture absorption rate of the thermosetting resin film is reduced, and the reliability of the package obtained using the first protective film is It improves more.
  • the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is heavy
  • the amount is preferably 600 to 1000 parts by mass with respect to 100 parts by mass of the content of the united component (A).
  • the content of the thermosetting component (B) is in such a range, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump, and the hard first protection It can form a film.
  • the content of the thermosetting component (B) be appropriately adjusted in accordance with the type of the polymer component (A) from the viewpoint that such effects can be obtained more remarkably.
  • the content of the thermosetting component (B) in the resin layer-forming composition (III) and the thermosetting resin film is the polymer component (A).
  • the amount is preferably 600 to 1000 parts by mass, more preferably 650 to 1000 parts by mass, and particularly preferably 650 to 950 parts by mass with respect to 100 parts by mass of the content of
  • the content of the thermosetting component (B) in the resin layer-forming composition (III) and the thermosetting resin film is the polymer component (B).
  • the amount is preferably 700 to 1000 parts by mass, more preferably 750 to 1000 parts by mass, and particularly preferably 750 to 900 parts by mass with respect to 100 parts by mass of the content of A).
  • Hardening accelerator (C) It is preferable that the composition for resin layer formation (III) and the thermosetting resin film contain a hardening accelerator (C).
  • a hardening accelerator (C) is a component for adjusting the hardening speed of composition (III) for resin layer formation.
  • Preferred curing accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (one or more hydrogen atoms are not hydrogen atoms Imidazoles substituted with the following groups: organic phosphines such as tributyl phosphine, diphenyl phosphine, triphenyl phosphine (phosphines in which one or more hydrogen atoms are substituted with an organic group); tetraphenyl phosphonium tetraphenyl borate Tetraphenyl boron salts such as triphenyl phos
  • the curing accelerator (C) contained in the resin layer-forming composition (III) and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination thereof and The ratio can be selected arbitrarily.
  • the content of the curing accelerator (C) is the content 100 mass of the thermosetting component (B)
  • the amount is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass.
  • the effect by using a hardening accelerator (C) is acquired more notably by the said content of a hardening accelerator (C) being more than the said lower limit.
  • the high-polarity curing accelerator (C) adheres to the thermosetting resin film under high temperature and high humidity conditions. The effect of suppressing migration and segregation to the adhesion interface side with the body is enhanced, and the reliability of the package obtained using the first protective film is further improved.
  • the composition for forming a resin layer (III) and the thermosetting resin film preferably contain a filler (D).
  • the first protective film containing the filler (D) facilitates adjustment of the thermal expansion coefficient. For example, by optimizing the thermal expansion coefficient of the first protective film with respect to the semiconductor chip, the reliability of the package obtained using the first protective film is further improved.
  • the first protective film containing the filler (D) can also reduce the moisture absorption rate or improve the heat dissipation.
  • the filler (D) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
  • Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide, boron nitride, etc .; spherical beads of these inorganic fillers; surface modification of these inorganic fillers Articles: single crystal fibers of these inorganic fillers; glass fibers and the like.
  • the inorganic filler is preferably silica or alumina.
  • the filler (D) contained in the resin layer-forming composition (III) and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination and ratio thereof Is optional.
  • the average particle diameter of the filler (D) is preferably 6 ⁇ m or less, and may be, for example, any of 4 ⁇ m or less, 2 ⁇ m or less, and 0.5 ⁇ m or less.
  • average particle diameter means the value of the particle diameter (D 50 ) at an integrated value of 50% in the particle size distribution curve determined by the laser diffraction scattering method, unless otherwise specified. .
  • the lower limit of the average particle diameter of the filler (D) is not particularly limited.
  • the average particle diameter of the filler (D) is preferably 0.01 ⁇ m or more in that it is easier to obtain the filler (D).
  • the average particle diameter of the filler (D) can be appropriately adjusted so as to fall within the range set by arbitrarily combining the above lower limit value and any upper limit value.
  • the average particle diameter of the filler (D) is preferably 0.01 to 6 ⁇ m, and for example, any of 0.01 to 4 ⁇ m, 0.01 to 2 ⁇ m, and 0.01 to 0.5 ⁇ m. May be However, this is an example of the preferable average particle diameter of filler (D).
  • the ratio of the content of the filler (D) to the total content of all the components other than the solvent (that is, the thermosetting resin is more preferably 3 to 30% by mass, and still more preferably 4 to 20% by mass. Particularly preferred is 5 to 15% by mass.
  • the composition for resin layer formation (III) and the thermosetting resin film may contain a coupling agent (E).
  • a coupling agent (E) having a functional group capable of reacting with an inorganic compound or an organic compound By using a coupling agent (E) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesion and adhesiveness of the thermosetting resin film to the adherend can be improved. Moreover, water resistance improves the 1st protective film containing a coupling agent (E), without impairing heat resistance.
  • the coupling agent (E) is preferably a compound having a functional group capable of reacting with a functional group possessed by the polymer component (A), the thermosetting component (B) or the like, and is preferably a silane coupling agent. More preferable.
  • silane coupling agent examples include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino) Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyl Trimethoxysi
  • composition for forming a resin layer (III) and the coupling agent (E) contained in the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination thereof and The ratio can be selected arbitrarily.
  • the content of the coupling agent (E) in the resin layer-forming composition (III) and the thermosetting resin film is the polymer component (A) and the thermosetting component ( It is preferable that it is 0.03-20 mass parts with respect to 100 mass parts of total content of B), It is more preferable that it is 0.05-10 mass parts, It is 0.1-5 mass parts Is particularly preferred.
  • the content of the coupling agent (E) is at least the lower limit value, the dispersibility of the filler (D) in the resin is improved, and the adhesion of the thermosetting resin film to the adherend is improved. The effect of using the coupling agent (E) is more remarkably obtained. Moreover, generation
  • Crosslinking agent (F) When using what has functional groups, such as a vinyl group which can couple
  • the article (III) and the thermosetting resin film may contain a crosslinking agent (F).
  • a crosslinking agent (F) is a component for making the said functional group in a polymer component (A) couple
  • crosslinking agent (F) for example, organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate type crosslinking agents (crosslinking agents having a metal chelate structure), aziridine type crosslinking agents (crosslinking agents having an aziridinyl group), etc. Can be mentioned.
  • organic polyvalent isocyanate compound for example, an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound etc.” Abbreviated in some cases); trimers such as the above-mentioned aromatic polyvalent isocyanate compounds, isocyanurates and adducts; terminal isocyanate urethane prepolymers obtained by reacting the above-mentioned aromatic polyvalent isocyanate compounds and the like with a polyol compound Etc.
  • aromatic polyvalent isocyanate compound etc Abbreviated in some cases
  • trimers such as the above-mentioned aromatic polyvalent isocyanate compounds, isocyanurates and adducts
  • terminal isocyanate urethane prepolymers obtained by reacting the above-mentioned aromatic polyvalent isocyanate compounds and the like with a polyol compound Et
  • the “adduct” includes the above-mentioned aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound or alicyclic polyvalent isocyanate compound, and low contents such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil It means a reactant with a molecule active hydrogen-containing compound.
  • the adduct include xylylene diisocyanate adduct of trimethylolpropane as described later, and the like.
  • the "terminal isocyanate urethane prepolymer" is as described above.
  • organic polyvalent isocyanate compound for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 Diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate in the hydroxyl groups of all or part of a polyol such as propane Or two or more compounds are added; lysine diisocyanate.
  • a polyol such as propane Or two or
  • organic polyhydric imine compound examples include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinyl propionate, and tetramethylolmethane.
  • a crosslinking agent (F) When using an organic polyhydric isocyanate compound as a crosslinking agent (F), it is preferable to use a hydroxyl-containing polymer as a polymer component (A).
  • a crosslink structure is formed on the thermosetting resin film by the reaction of the crosslinking agent (F) with the polymer component (A). It can be introduced easily.
  • composition (III) for resin layer formation and the crosslinking agent (F) contained in the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination and ratio thereof Is optional.
  • the content of the crosslinking agent (F) is 100 parts by mass of the content of the polymer component (A)
  • the amount is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass.
  • the effect by using a crosslinking agent (F) is acquired more notably by the said content of a crosslinking agent (F) being more than the said lower limit.
  • the excess use of a crosslinking agent (F) is suppressed because the said content of a crosslinking agent (F) is below the said upper limit.
  • thermosetting resin (G) The composition for resin layer formation (III) and the thermosetting resin film may contain an energy ray curable resin (G).
  • a thermosetting resin film can change a characteristic by irradiation of an energy ray by containing energy ray curable resin (G).
  • the energy ray-curable resin (G) is obtained by polymerizing (curing) an energy ray-curable compound.
  • the energy ray curable compound include a compound having at least one polymerizable double bond in the molecule, and an acrylate compound having a (meth) acryloyl group is preferable.
  • acrylate compound examples include trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol monohydroxy penta
  • Linear aliphatic skeleton-containing (meth) acrylates such as meta) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; Cycloaliphatic skeleton-containing (meth) acrylates such as cyclopentanyl di (meth) acrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate Oligoester (meth)
  • the weight average molecular weight of the energy ray curable compound is preferably 100 to 30,000, and more preferably 300 to 10,000.
  • the energy ray-curable compound used for the polymerization may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the energy ray curable resin (G) contained in the resin layer forming composition (III) and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, Combinations and ratios can be selected arbitrarily.
  • the ratio of the content of the energy ray-curable resin (G) to the total mass of the composition (III) for forming a resin layer Is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass.
  • Photoinitiator (H) When the composition for forming a resin layer (III) and the thermosetting resin film contain an energy ray-curable resin (G), photopolymerization is performed to efficiently promote the polymerization reaction of the energy ray-curable resin (G). You may contain the initiator (H).
  • Examples of the photopolymerization initiator (H) in the composition (III) for forming a resin layer include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin benzoate Benzoin compounds such as dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one; Acyl phosphine oxide compounds such as 2,4,6-trimethyl benzoyl) phenyl phosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; benzyl phenyl sulfide, tetramethyl Sulfide compounds such as uram monosulfide; ⁇ -ketol compounds
  • composition (III) for forming a resin layer and the photopolymerization initiator (H) contained in the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination thereof And the ratio can be selected arbitrarily.
  • the content of the photopolymerization initiator (H) in the resin layer-forming composition (III) and the thermosetting resin film is the content of the energy ray-curable resin (G)
  • the amount is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass with respect to 100 parts by mass.
  • the composition for forming a resin layer (III) and the thermosetting resin film may contain a colorant (I).
  • the colorant (I) is, for example, a component for imparting an appropriate light transmittance to the thermosetting resin film and the first protective film.
  • the colorant (I) may be known and may be, for example, any of a dye and a pigment.
  • the dyes may be any of acid dyes, reactive dyes, direct dyes, disperse dyes, cationic dyes and the like.
  • the colorant (I) contained in the resin layer-forming composition (III) and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination and ratio thereof Is optional.
  • the content of the coloring agent (I) of the composition (III) for forming a resin layer is such that the visible light transmittance and the infrared transmittance of the thermosetting resin film become the target values.
  • the content of the coloring agent (I) depends on the type of the coloring agent (I) or, in the case of using two or more kinds of coloring agents (I) in combination, depending on the combination of the coloring agent (I), etc. And may be adjusted as appropriate.
  • the ratio of the content of the colorant (I) to the total content of all components other than the solvent in the resin layer-forming composition (III) that is, heat curing
  • the ratio of the content of the colorant (I) to the total mass of the thermosetting resin film in the transparent resin film is preferably 0.01 to 10% by mass.
  • the composition for forming a resin layer (III) and the thermosetting resin film may contain a general-purpose additive (J) within the range not impairing the effects of the present invention.
  • the general-purpose additive (J) may be a known one, can be optionally selected according to the purpose, and is not particularly limited. Preferred examples thereof include a plasticizer, an antistatic agent, an antioxidant, a gettering agent, etc. Can be mentioned.
  • the general-purpose additive (J) contained in the resin layer-forming composition (III) and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination thereof and The ratio can be selected arbitrarily.
  • the content of the general-purpose additive (J) in the composition for forming a resin layer (III) and the thermosetting resin film is not particularly limited, and may be appropriately selected depending on the purpose.
  • the composition for forming a resin layer (III) preferably further contains a solvent.
  • the composition for forming a resin layer (III) containing a solvent has good handleability.
  • the solvent is not particularly limited, but preferred examples thereof include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), 1-butanol and the like Esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methyl pyrrolidone.
  • the solvent contained in the resin layer-forming composition (III) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the solvent contained in the resin layer-forming composition (III) is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the resin layer-forming composition (III) can be mixed more uniformly.
  • the content of the solvent in the composition for forming a resin layer (III) is not particularly limited, and may be appropriately selected, for example, according to the types of components other than the solvent.
  • the composition (III) for forming a resin layer and the thermosetting resin film contain the polymer component (A) and the thermosetting component (B), contain polyvinyl acetal as the polymer component (A), and are epoxy It is preferable to contain a liquid thing as resin (B1), and what further contains a hardening accelerator (C) and a filler (D) other than these components is more preferable. And it is preferable that the filler (D) in this case has the above-mentioned average particle diameter.
  • composition (III) for forming a resin layer for example, a polymer component (A) which is a polyvinyl acetal, a liquid epoxy resin (B1), a thermosetting agent (B2), and curing It contains an accelerator (C) and a filler (D), and in the composition (III) for forming a resin layer, the total content of the epoxy resin (B1) and the thermosetting agent (B2) is the above-mentioned content.
  • the content of the curing accelerator (C) is the epoxy resin (B1) and the thermosetting agent (B2) And 0.1 to 5 parts by mass with respect to 100 parts by mass of the filler, and the filler (D) with respect to the total content of all the components other than the solvent in the composition for forming a resin layer (III)
  • the content ratio of the filler is 3 to 30% by mass, and the filler (D
  • the average particle diameter of include those at 6 ⁇ m or less.
  • the composition (III) for forming a resin layer for example, a polymer component (A) which is a polyvinyl acetal, a liquid epoxy resin (B1), and a thermosetting agent (B2), A curing accelerator (C) and a filler (D), the weight average molecular weight of the polyvinyl acetal is 40000 or less, the weight average molecular weight of the epoxy resin (B1) is 10000 or less, and a resin layer In the composition for formation (III), the total content of the epoxy resin (B1) and the thermosetting agent (B2) is 600 to 1000 parts by mass with respect to 100 parts by mass of the content of the polymer component (A).
  • the content of the curing accelerator (C) is 0.1 to 5 parts by mass with respect to 100 parts by mass of the total content of the epoxy resin (B1) and the thermosetting agent (B2).
  • resin layer type In the composition (III) the ratio of the content of the filler (D) to the total content of all the components other than the solvent is 5 to 15% by mass, and the average particle diameter of the filler (D) is What is 2 micrometers or less is mentioned.
  • composition for forming a thermosetting resin film such as the composition for forming a resin layer (III) can be obtained by blending the respective components for constituting the composition .
  • a solvent it may be used by mixing the solvent with any compounding component other than the solvent and diluting this compounding component in advance, or by previously diluting any compounding component other than the solvent A solvent may be used by mixing with these compounding ingredients without storage.
  • the method of mixing each component at the time of compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer; a method of adding ultrasonic waves and mixing, etc. It may be selected as appropriate.
  • the temperature and time of addition and mixing of the respective components are not particularly limited as long as the respective blended components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.
  • composition for forming energy ray curable resin film ⁇ Composition for forming resin layer (IV)
  • a composition for forming an energy ray-curable resin film (IV) containing an energy ray-curable component (a) in the present specification, simply “resin layer And the like, which may be abbreviated as “forming composition (IV)”.
  • the energy ray curable component (a) is a component which is cured by irradiation of energy rays, and is also a component for imparting film forming property, flexibility and the like to the energy ray curable resin film.
  • the energy ray curable component (a) includes, for example, an energy ray curable group, a polymer (a1) having a weight average molecular weight of 80000 to 2,000,000, and an energy ray curable group having a molecular weight of 100 to 80,000. Compound (a2) is mentioned.
  • the polymer (a1) may be at least partially crosslinked by a crosslinking agent, or may be non-crosslinked.
  • Examples of the polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000 include an acrylic polymer (a11) having a functional group capable of reacting with a group possessed by another compound, Acrylic resin (a1-1) formed by polymerizing an energy ray curable compound (a12) having a group reactive with a functional group and an energy ray curable group such as an energy ray curable double bond .
  • Examples of the functional group capable of reacting with a group possessed by another compound include, for example, a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom Groups), epoxy groups and the like.
  • the functional group is preferably a group other than a carboxy group.
  • the functional group is preferably a hydroxyl group.
  • acrylic polymer (a11) having a functional group examples include those obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer having no functional group. In addition to the monomers, monomers (non-acrylic monomers) other than acrylic monomers may be copolymerized.
  • the acrylic polymer (a11) may be a random copolymer or a block copolymer.
  • the acrylic monomer having the functional group, the acrylic monomer having no functional group, and the non-acrylic monomer may be used alone or in combination of two or more. More than one species may be used in combination, and when two or more species are used in combination, their combination and ratio can be arbitrarily selected.
  • the energy ray curable compound (a12) is one or two selected from the group consisting of an isocyanate group, an epoxy group and a carboxy group as a group capable of reacting with the functional group possessed by the acrylic polymer (a11) What has the above is preferable, and what has an isocyanate group as said group is more preferable.
  • the energy beam curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.
  • Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80,000 include a group containing an energy ray-curable double bond, and preferred examples thereof Acryloyl group, a vinyl group etc. are mentioned.
  • composition for forming a resin layer (IV) and the energy ray-curable resin film contain the compound (a2) as the energy ray-curable component (a), a polymer having no energy ray-curable group ( It is preferable to also contain b).
  • the polymer (b) may be at least partially crosslinked by a crosslinking agent, or may be non-crosslinked.
  • polymer (b) having no energy ray curable group examples include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, acrylic urethane resins, and the like.
  • the polymer (b) is preferably an acrylic polymer (sometimes referred to as “acrylic polymer (b-1)” in the present specification).
  • composition (IV) for forming a resin layer examples include those containing one or both of the polymer (a1) and the compound (a2). And when the composition (IV) for resin layer formation contains the said compound (a2), it is preferable to also contain the polymer (b) which does not have an energy ray curable group further, and in this case, the said weight is further added. It is also preferable to contain a united body (a1). In addition, the composition for forming a resin layer (IV) contains neither the compound (a2) but the polymer (a1) and the polymer (b) having no energy ray curable group. It is also good.
  • the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group may be used alone, respectively. Two or more types may be used in combination, and when two or more types are used in combination, their combination and ratio can be arbitrarily selected.
  • the composition for resin layer formation (IV) contains the polymer (a1), the compound (a2) and the polymer (b) having no energy ray curable group
  • the composition for resin layer formation (IV) In the above, the content of the compound (a2) is 10 to 400 parts by mass with respect to 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray curable group. Is preferred.
  • the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (Ie, the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group in the energy ray-curable resin film relative to the total mass of the energy ray-curable resin film is preferably 5 to 90% by mass.
  • the composition for forming a resin layer (IV) may contain, according to the purpose, a thermosetting component, a photopolymerization initiator, a filler, a coupling agent, a crosslinking agent, a coloring agent, and a general-purpose addition, in addition to the energy ray curable component. It may contain one or more selected from the group consisting of an agent and a solvent.
  • a thermosetting component a photopolymerization initiator
  • a filler e.g., a thermosetting component
  • a coupling agent e.g., a crosslinking agent
  • a coloring agent e.g., a coloring agent
  • a general-purpose addition e.g., a general-purpose addition, in addition to the energy ray curable component. It may contain one or more selected from the group consisting of an agent and a solvent.
  • the energy ray-curable resin film formed has an adhesive force to an adherend by heating. The strength of the first protective film formed from the energy ray
  • thermosetting component As the thermosetting component, the photopolymerization initiator, the filler, the coupling agent, the crosslinking agent, the colorant, the general-purpose additive and the solvent in the composition (IV) for forming a resin layer, a composition for forming a resin layer (III) thermosetting component (B), photopolymerization initiator (H), filler (D), coupling agent (E), crosslinking agent (F), colorant (I), general purpose additive (J And the same as the solvent.
  • thermosetting component In the composition (IV) for forming a resin layer, the thermosetting component, the photopolymerization initiator, the filler, the coupling agent, the crosslinking agent, the crosslinking agent, the coloring agent, the general-purpose additive and the solvent are each used alone. When using together 2 or more types and 2 or more types together, those combinations and ratios can be selected arbitrarily.
  • the content of the thermosetting component, the photopolymerization initiator, the filler, the coupling agent, the crosslinking agent, the coloring agent, the general-purpose additive and the solvent in the composition (IV) for forming a resin layer is appropriately adjusted according to the purpose. There is no particular limitation as long as the
  • composition for forming an energy ray-curable resin film such as the composition for forming a resin layer (IV)
  • the composition for forming an energy ray-curable resin film is obtained by blending the components for constituting the composition can get. There is no particular limitation on the order of addition of each component at the time of blending, and two or more components may be added simultaneously.
  • a solvent it may be used by mixing the solvent with any compounding component other than the solvent and diluting this compounding component in advance, or by previously diluting any compounding component other than the solvent A solvent may be used by mixing with these compounding ingredients without storage.
  • the method of mixing each component at the time of compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer; a method of adding ultrasonic waves and mixing, etc. It may be selected as appropriate.
  • the temperature and time of addition and mixing of the respective components are not particularly limited as long as the respective blended components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.
  • a method of manufacturing a semiconductor chip with a first protective film of the present invention is a method of manufacturing a semiconductor chip with a first protective film described above, and the method of manufacturing the semiconductor chip with a first protective film Forming a first protective film by attaching a curable resin film (which may be abbreviated as "adhering step” in the present specification) and curing the curable resin film after application;
  • a step sometimes abbreviated "first protective film forming step” in the present specification
  • a step of obtaining a semiconductor chip by dividing the semiconductor wafer the “division step” in the present specification
  • the head of the bump such that the value of the S (C) / S (Sn) is 0.32 or less Above the top
  • the S (C) / S (Sn) value may be 0.32 or less on the bumps.
  • FIG. 5 is an enlarged cross-sectional view for schematically describing the present embodiment.
  • the attaching process is performed, and as shown in FIG. 5A, the curable resin film 13 ′ is attached to the bump forming surface 9a of the semiconductor wafer 9 ′.
  • the curable resin film 13 'spreads between the large number of bumps 91 and adheres to the bump forming surface 9a, and at the same time, the surface 91a of the bumps 91, particularly the vicinity of the bump forming surface 9a. It is possible to cover the surface 91 a and embed the bumps 91 so as to cover these areas.
  • the top portion 910 of the bump 91 of the semiconductor wafer 9 ′ penetrates the curable resin film 13 ′ and protrudes from the curable resin film 13 ′.
  • the curable resin film 13 ′ may be used alone, but as shown here, the first support sheet 10 and the curable resin film 13 formed on the first support sheet 10 It is preferable to use the first protective film forming sheet 191 configured to include '.
  • the first protective film forming sheet 191 configured to include '.
  • the first step is to attach the curable resin film in the sheet for forming a first protective film to the bump forming surface of the semiconductor wafer.
  • the protective film forming sheet itself may be attached to the bump forming surface of the semiconductor wafer.
  • laminated structure (1) a structure in which a sheet for forming a first protective film is attached to a bump forming surface of a semiconductor wafer.
  • the first support sheet 10 is configured to include the first base 11 and the buffer layer 12 formed on the first base 11. That is, the first protective film-forming sheet 191 is configured by laminating the first base material 11, the buffer layer 12, and the curable resin film 13 'in this order in the thickness direction.
  • FIG. 6 is an enlarged cross-sectional view schematically showing the first protective film formation sheet 191. As shown in FIG.
  • the first support sheet 10 As the first support sheet 10, a known one can be used.
  • the first substrate 11 is in the form of a sheet or a film, and examples of the constituent material thereof include various resins.
  • the resin include polyethylenes such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE); polyethylene other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene and norbornene resin Polyolefins; Ethylene copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer (ethylene as monomer Copolymers obtained by using a vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (resin obtained by using vinyl chloride as a monomer), polystyrene, polycycloolefin, polyethylene terephthalate, polyethylene Nafta Polyesters
  • the polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
  • the resin for example, a crosslinked resin obtained by crosslinking one or more of the above-described resins exemplified so far; modification of an ionomer using one or more of the above-described resins exemplified so far Resin is also mentioned.
  • the resin constituting the first substrate 11 may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the first substrate 11 may be only one layer (single layer) or may be a plurality of layers of two or more layers, and in the case of a plurality of layers, the plurality of layers may be the same or different from each other.
  • the combination is not particularly limited.
  • the thickness of the first substrate 11 is preferably 25 to 150 ⁇ m.
  • the thickness of the first base material 11 means the thickness of the entire first base material 11, and for example, the thickness of the first base material 11 composed of a plurality of layers refers to the first base material 11 Means the total thickness of all the layers that make up.
  • the buffer layer 12 has a buffering action on the force applied to the buffer layer 12 and the layer adjacent thereto.
  • the curable resin film 13 ′ is shown.
  • the buffer layer 12 is in the form of a sheet or a film, and is preferably energy ray curable.
  • the energy ray-curable buffer layer 12 can be more easily peeled off from a curable resin film 13 'described later by energy ray curing.
  • the constituent material of the buffer layer 12 As a constituent material of the buffer layer 12, various adhesive resins are mentioned, for example.
  • the constituent materials thereof When the buffer layer 12 is energy ray curable, the constituent materials thereof also include various components necessary for energy ray curing.
  • the buffer layer 12 may be only one layer (single layer) or may be a plurality of layers of two or more layers, and in the case of multiple layers, these multiple layers may be the same or different from one another, and the combination of these multiple layers is It is not particularly limited.
  • the thickness of the buffer layer 12 is preferably 60 to 675 ⁇ m.
  • the thickness of the buffer layer 12 means the entire thickness of the buffer layer 12, and, for example, the thickness of the buffer layer 12 composed of a plurality of layers is the total of all the layers constituting the buffer layer 12. Means the thickness of.
  • the thermosetting resin film 13 ' can be attached to the bump forming surface 9a by pressure bonding to the bump forming surface 9a of the semiconductor wafer 9'.
  • the attaching step it is preferable to attach the curable resin film 13 'to the bump forming surface 9a while heating. In this manner, the generation of the void is caused between the curable resin film 13 'and the bump forming surface 9a and between the curable resin film 13' and the surface 91a of the bump 91. It can suppress more. Finally, at the top of the bump, the effect of suppressing the remaining of the first protective film residue becomes higher.
  • the heating temperature of the curable resin film 13 'at this time is not required to be an excessively high temperature, and is preferably, for example, 60 to 100.degree.
  • “excessive high temperature” means, for example, when the curable resin film 13 ′ is thermosetting, the thermosetting of the curable resin film 13 ′ proceeds, etc., to the curable resin film 13 ′. It means the temperature at which an unintended effect appears.
  • the pressure applied to the curable resin film 13 ′ (sometimes referred to as “sticking pressure” in the present specification) is 0.
  • the pressure is preferably in the range of 3 to 1 MPa.
  • the laminated structure (1) 101 may be used as it is in the next step, but if necessary, the bump forming surface 9a of the semiconductor wafer 9 '
  • the thickness of the semiconductor wafer 9 ' may be adjusted by grinding the opposite surface (back surface) 9b. Grinding of the back surface 9b of the semiconductor wafer 9 'can be performed by a known method such as a method using a grinder.
  • the thickness of the portion excluding the bumps of the semiconductor wafer 9' is the same as the thickness of the portion excluding the bumps of the semiconductor chip described above. preferable.
  • the thickness of the portion excluding the bumps of the semiconductor wafer 9' before grinding is preferably 400 to 1200 ⁇ m, and more preferably 650 to 780 ⁇ m. .
  • the first support sheet 10 is peeled off from the thermosetting resin film 13 ′ in the laminated structure (1) 101.
  • the back surface 9 b of the semiconductor wafer 9 ′ is ground, it is preferable to peel off the first support sheet 10 after the grinding.
  • a laminated structure (2) is provided, which is provided with a thermosetting resin film 13 'on the bump formation surface 9a of the semiconductor wafer 9'. That is, a semiconductor wafer with a curable resin film is obtained.
  • the buffer layer 12 is energy ray curable
  • the buffer layer 12 is cured by irradiation of energy rays to reduce the adhesiveness of the buffer layer 12, and then the first thermosetting resin film 13 ′ is removed from the thermosetting resin film 13 ′. It is preferable to peel off the support sheet 10.
  • the first protective film forming step is performed after the sticking step, and as shown in FIG. 5C, the first protective film 13 is cured by curing the curable resin film 13 ′ after the sticking.
  • a 1st protective film formation process can be performed after peeling of the above-mentioned 1st support sheet 10.
  • the first protective film forming step can be performed after the grinding of the back surface 9b.
  • the curing conditions of the curable resin film 13 ′ are not particularly limited as long as the first protective film has a curing degree sufficient to exhibit its function, and may be appropriately selected according to the type of the thermosetting resin film. Good.
  • the heating temperature is preferably 100 to 180 ° C. and the heating time is 0.5 to 5 hours at the time of thermosetting of the curable resin film 13'. Is preferred.
  • the curable resin film 13 ′ may be pressurized, and in this case, the pressure is preferably 0.3 to 1 MPa.
  • the illuminance of the energy ray is preferably 180 to 280 mW / cm 2 at the time of energy ray curing of the curable resin film 13'.
  • the light quantity is preferably 450 to 1500 mJ / cm 2 .
  • the dividing step is performed after the step of forming the first protective film, and as shown in FIG. 5D, the semiconductor wafer 9 'is divided to obtain the semiconductor chip 9.
  • the semiconductor chip 1 with a first protective film, which is an object, is obtained.
  • the division of the semiconductor wafer 9 ' can be performed by a known method.
  • the back surface 9b of the semiconductor wafer 9' in the laminated structure (3) (semiconductor wafer with first protective film) 103 is used.
  • a dicing sheet (or dicing tape) may be attached, and thereafter dicing may be performed by a known method.
  • laminated structure (5) a structure in which the first protective film is provided on the bump formation surface of the semiconductor wafer and the dicing sheet is provided on the back surface of the semiconductor wafer. It may be called.
  • the semiconductor wafer in this laminated structure (5) may be singulated together with the first protective film, and a semiconductor chip may be formed, which may be referred to as "laminated structure (6)".
  • the layer in contact with the object to be attached (for example, a semiconductor chip) is energy ray curable as the dicing sheet
  • this layer is cured by irradiation of energy rays after dicing and tackiness is obtained.
  • the dicing sheet can be more easily removed from the object to be attached.
  • a second protective film-forming sheet may be used in place of the above-described dicing sheet.
  • the second protective film-forming sheet has a configuration in which a protective film-forming film for forming the above-mentioned second protective film on the back surface of the semiconductor chip is formed on the dicing sheet.
  • the dicing sheet is removed after dicing, and finally, a semiconductor chip in a state in which the second protective film is attached to the back surface is obtained. That is, the semiconductor chip with a first protective film provided with the second protective film on the back surface of the semiconductor chip described above can be obtained by such a manufacturing method.
  • the residual of the first protective film residue is suppressed at the top portion 910 of the bump 91 as described above immediately after the step of forming the first protective film. Therefore, in the top portion 910 of the bump 91 of the semiconductor chip 1 with a first protective film, which is the object, the remaining of the first protective film residue is suppressed.
  • the curable resin film 13 ′ it is preferable to use one which hardly leaves the residue on the top portion 910 of the bump 91. Then, in the attaching process, the top portion 910 of the bump 91 may be protruded from the curable resin film 13 ′ such that the S (C) / S (Sn) value is 0.32 or less.
  • curable resin film 13 which is easy to acquire the effect of such this invention notably, what was demonstrated previously is mentioned. That is, in the case of a thermosetting resin film, as the composition (III) for forming a resin layer, one having a small weight average molecular weight of a resin component such as a polymer component (A) or an epoxy resin (B1), It is preferable to use one having a range in which the average particle diameter of the filler (D) is small, one having a range in which the content of the filler (D) is small, and the like. As an epoxy resin (B1), it is preferable to use what is liquid at normal temperature.
  • a resin component such as a polymer component (A) or an epoxy resin (B1)
  • an epoxy resin (B1) it is preferable to use what is liquid at normal temperature.
  • the residue reduction step is a step of reducing the amount of residue on the bumps 91 so that the value of the S (C) / S (Sn) becomes 0.32 or less after the attachment step. is there. More specifically, the residue reduction step is performed at any stage after the attaching step until the target semiconductor chip with a protective film is obtained. Then, in the residue reduction step, for example, a residue such as a curable resin film residue or a first protective film residue remaining on the top portion 910 of the bump 91 of the semiconductor wafer 9 ′ or the semiconductor chip 9.
  • reduce the amount of means that the amount of residue is small to such an extent that the effect is not recognized even if the residue is not present or is present. means.
  • a residue reducing step is performed after the first protective film forming step to reduce the amount of the first protective film residue on the bumps 91.
  • FIG. 7 is an enlarged cross-sectional view for schematically explaining an example of the residue reduction step in the present embodiment.
  • the first protective film after completion of the first protective film forming step, the first protective film remains on the top portion 910 of the bumps 91 in the laminated structure (3) (semiconductor wafer with first protective film) 103 described above.
  • the object 131 may remain.
  • FIG. 7 (a) shows such a laminated structure (3), and the laminated structure (3) 103 is the same as the laminated structure (3) 103 in FIG. The difference is that the remaining amount of the object 131 is large.
  • the upper portion of the bump 91 of the semiconductor wafer 9 ′ in the laminated structure (3) 103 is irradiated with plasma to leave the first protective film remaining on the upper portion of the bump 91. Reduce the amount of objects 131.
  • FIG. 7B a laminated structure in which the remaining of the first protective film residue 131 is suppressed in the top portion 910 of the bumps 91 as in the case shown in FIG. 5C. Get the body.
  • a product obtained by performing the residue reduction step on the laminated structure (3) in this manner may be referred to as a laminated structure (4).
  • reference numeral 104 is given to indicate the laminated structure (4).
  • the irradiation conditions of the plasma in the residue reduction step are not particularly limited as long as the amount of the first protective film residue 131 can be sufficiently reduced.
  • the pressure of the gas is 80 to 120 Pa
  • the applied power is 200 to 300 W
  • the plasma is irradiated for 0.5 to 5 minutes in the presence of a reactive gas such as tetrafluoromethane (CF 4 ) gas or oxygen gas.
  • CF 4 tetrafluoromethane
  • the irradiation range of plasma in the residue reduction step is not particularly limited as long as the amount of the first protective film residue 131 can be sufficiently reduced, and at least the upper portion of the bump 91 may be included. Then, in the residue reduction step, for example, plasma may be irradiated on the entire surface of the semiconductor wafer 9 ′ provided with the first protective film 13 on the side having the bumps 91.
  • the residue reduction step in the present embodiment may be performed after the division step.
  • the object to be irradiated with plasma in this case is not the semiconductor wafer 9 'but the semiconductor chip 9 (in other words, with the first protective film in which the first protective film residue 131 remains, not the laminated structure (3) 103) It becomes a semiconductor chip 1).
  • a residue reduction process can be performed by the same method as the above-mentioned case except this point.
  • the fine particles may collide with at least the upper portion of the bumps 91, and the range in which the fine particles collide can be made similar to the above-described irradiation range of plasma.
  • the fine particles are not particularly limited as long as the amount of the first protective film residue 131 can be reduced, and specific examples thereof include abrasives made of an inorganic material such as silica sand, alumina, glass, etc .; dry ice fine particles etc. Can be mentioned. Among these, it is preferable that the fine particles are dry ice fine particles in that the remaining of the fine particles in the semiconductor chip with the first protective film can be remarkably easily suppressed by the vaporization.
  • FIG. 8 is an enlarged cross-sectional view for schematically illustrating another example of the residue reduction step in the present embodiment.
  • the curable resin film residue 131 ′ is present on the top portion 910 of the bumps 91 in the laminated structure (2) (semiconductor wafer with curable resin film) 102 described above. It may remain.
  • FIG. 8 (a) shows such a laminated structure (2), and the laminated structure (2) 102 is the same as the laminated structure (2) 102 in FIG. The difference is that the remaining amount of the object 131 ′ is large.
  • the upper portion of at least the bumps 91 of the semiconductor wafer 9 ′ in the laminated structure (2) 102 is irradiated with plasma to form a curable resin film on the upper portions of the bumps 91. Reduce the amount of residue 131 '.
  • FIG. 8 (b) in the same manner as shown in FIG. 5 (b), in the top portion 910 of the bump 91, the lamination in which the remaining of the curable resin film residue 131 'is suppressed.
  • a structure is obtained.
  • a product obtained by performing the residue reduction step on the laminated structure (2) in this manner may be referred to as a laminated structure (10).
  • reference numeral 110 is attached to indicate the laminated structure (10).
  • the irradiation conditions of plasma in the present embodiment can be the same as the irradiation conditions described above except that the irradiation object is different.
  • the curable resin film residue 131 ′ instead of plasma irradiation is used, thereby the curable resin film residue is The amount of 131 'can be reduced. Also in this embodiment, the fine particles can be made to collide in the same manner as described above.
  • FIG. 9 is an enlarged cross-sectional view for schematically illustrating still another example of the residue reduction step in the present embodiment.
  • FIG. 9 (a) shows such a laminated structure (3), and the laminated structure (3) 103 is the same as the laminated structure (3) 103 in FIG. The difference is that the remaining amount of the object 131 is large.
  • the portion of the upper portion of the bump 91 of the semiconductor wafer 9 ′ in the laminated structure (3) 103 where the first protective film residue 131 remains is the first portion.
  • the protective film residue 131 is removed together. More specifically, in the laminated structure (3) 103, the bump 91 of the semiconductor wafer 9 'is cut at a specific distance below the vertex thereof, and the cut piece is removed to thereby form the first bump 91.
  • the upper part where the protective film residue 131 remains is removed together with the first protective film residue 131.
  • laminated-structure (11) 111 which the shape of bump changed is obtained.
  • a method of cutting a specific portion of the bump 91 there is a method of cutting the bump 91 using a dicing blade.
  • An ordinary dicing sheet can be used as the dicing sheet in this case.
  • the cutting of the specific portion of the bump 91 using a dicing blade can be performed by the same method as dicing of a normal semiconductor wafer except that the cutting portion is different.
  • the rotation speed of the blade is preferably 20000 to 45000 rpm
  • the feed speed (moving speed) of the blade is preferably 10 to 100 mm / s.
  • the first protective film is provided on the bump formation surface of the semiconductor wafer in the laminated structure (3) before the specific portion of the bump 91 is cut like this, and the back surface of the semiconductor wafer What is constituted by providing a dicing tape is sometimes referred to as "laminated structure (7)".
  • the cut site of the bump 91 in the residue reduction step is not particularly limited as long as the amount of the first protective film residue 131 can be sufficiently reduced.
  • the distance from the vertex of the bump is preferably any distance of 0.15 H to 0.4 H
  • the lower site more preferably, the lower site by any distance of 0.18 H to 0.35 H, and further preferably, the lower site by any distance of 0.21 H to 0.3 H, is the cut site of the bump. is there.
  • the portion specified in the above numerical range should be included in the cut portion. Is preferred.
  • the semiconductor chip 3 with the first protective film is obtained by performing the same process using the stacked structure (7) instead of the stacked structure (3) 103.
  • the laminated structure (7) the one in which the specific part of the bump is cut as described above is referred to as "laminated structure (8)", and further, in the laminated structure (8).
  • the semiconductor wafer may be singulated with the first protective film to form a semiconductor chip, which may be referred to as a “laminated structure (9)”.
  • the upper portion of the bump 91 is removed together with the first protective film residue 131, but depending on the conditions in any of the steps until the target semiconductor chip with the first protective film is obtained, a small amount of The first protective film residue 131 may remain on the top portion 920 of the bump 92.
  • the semiconductor chip with a first protective film in such a state is the semiconductor chip 4 with a first protective film shown in FIG.
  • the residue reduction step in the present embodiment is as described above, It may be performed after the dividing step.
  • the object to be cut in this case is not the bumps 91 of the semiconductor wafer 9 'but the bumps 91 of the semiconductor chip 9 (in other words, the first protective film residue 131 remains, not the laminated structure (3)). It becomes the semiconductor chip 1 with a protective film).
  • a residue reduction process can be performed by the same method as the above-mentioned case except this point. However, it is preferable to perform the residue reduction step in the present embodiment after the first protective film formation step and before the division step in that cutting of the specific portion of the bump 91 is easier.
  • FIG. 10 is an enlarged cross-sectional view for schematically illustrating still another example of the residue reduction step in the present embodiment.
  • the curable resin is applied to the top portion 910 of the bumps 91 in the laminated structure (2) (semiconductor wafer with curable resin film) 102 described above.
  • Film residue 131 ' may remain.
  • FIG. 10 (a) shows such a laminated structure (2), and the laminated structure (2) 102 is the same as the laminated structure (2) 102 in FIG. The difference is that the remaining amount of the object 131 ′ is large.
  • the portion of the upper portion of the bumps 91 of the semiconductor wafer 9 ′ in the laminated structure (2) 102 where the curable resin film residue 131 ′ remains is cured. Resin film residue 131 'together. More specifically, in the laminated structure (2) 102, the bumps 91 of the semiconductor wafer 9 'are cut at a specific distance below the apex thereof, and the cut pieces are removed, whereby the curability of the bumps 91 is achieved. The upper portion where the resin film residue 131 'remains is removed together with the curable resin film residue 131'. Thereby, as shown in FIG.10 (b), laminated-structure (12) 112 which the shape of bump changed is obtained.
  • the cutting conditions of the bumps 91 in the present embodiment can be the same as the cutting conditions described above, except that the object to be cut is different.
  • the manufacturing method of the semiconductor chip with the first protective film in which the top of the bump is a curved surface as shown in FIGS. 1 and 2, and the bumps as shown in FIGS. 3 and 4.
  • the manufacturing method of the semiconductor chip with a 1st protective film whose top of the head is a plane was explained.
  • the method of manufacturing the semiconductor chip with a first protective film, in which the top of the bump is flat removes a part of the bump of the semiconductor wafer or the semiconductor chip together with the residue adhering thereto. Process (residue reduction process).
  • the method of manufacturing a semiconductor chip with a first protective film without such a residue reduction process wastes a part of the bump and a part of the material used to form the first protective film.
  • the amount of removal of the bumps can be made the minimum necessary amount to achieve the purpose, and the excessive amount is suppressed It has the advantage of being able to
  • the semiconductor chip with a first protective film obtained by the manufacturing method not having the residue reduction step can be obtained by the first manufacturing method having the residue reduction step in that the height of the bumps can be easily increased. It is advantageous over a semiconductor chip with a protective film.
  • the semiconductor chip with a first protective film which needs to carry out a residue reduction step at the time of manufacture between the bump and the surface of a portion near the bump forming surface of the semiconductor chip and the first protective film, There is a tendency for fine gaps to easily occur. This is because, in the pasting process, when the residue of the curable resin film is likely to remain on the top of the bump, between the surface of the bump near the surface on which the bump is formed and the curable resin film, This is because a fine gap tends to be generated.
  • the semiconductor chip with the first protective film obtained by the manufacturing method not having the residue reduction step is advantageous in that the void portion is not easily generated and the protective effect by the first protective film is higher. .
  • the manufacturing method of the semiconductor chip with a first protective film shown in FIGS. 1 to 4 has been mainly described, but other semiconductor chips with a first protective film are also required other processes based on their structures.
  • it can manufacture suitably by the manufacturing method which has separately at suitable timing.
  • the evaluation method of the semiconductor chip and first protective film laminate of the present invention is formed on the semiconductor chip and the surface (bump formation surface) of the semiconductor chip having bumps.
  • An evaluation method of a semiconductor chip and a first protective film stack comprising: a first protective film, wherein an energy dispersive type X is applied to a top of the bump in the semiconductor chip and the first protective film stack.
  • the semiconductor chip / first protective film laminate is determined to be a target semiconductor chip with a first protective film, and the value of S (C) / S (Sn) Is larger than 0.32, the semiconductor chip It is determined that the semiconductor chip / first protective film laminate is not a target semiconductor chip with a first protective film.
  • EDX line spectroscopy
  • the semiconductor chip / first protective film laminate is the same as the above-described semiconductor chip with a first protective film except that the S (C) / S (Sn) value is not specified, and S (C (C) Depending on the result of specifying the / S (Sn) value, the semiconductor chip with the first protective film may be or may be other than that.
  • the semiconductor chip / first protective film laminate to be evaluated is the semiconductor chip with the first protective film of the present invention described above It can be determined. Then, whether or not the semiconductor chip / first protective film laminate can increase the bonding strength between the bumps and the substrate, and the degree of electrical connection in the joined body of the semiconductor chip and the substrate It can be determined whether (conductivity) can be increased.
  • the EDX analysis of the top of the bump in the semiconductor chip / first protective film laminate is the case of the EDX analysis of the top of the bump in the semiconductor chip with the first protective film described above. And can be done in the same way.
  • the semiconductor chip / first protective film laminate before the determination has a small S (C) / S (Sn) value to such an extent that it is determined to be the semiconductor chip with the first protective film, for example, as shown in FIGS. It has the same configuration as the semiconductor chip with a first protective film shown.
  • the semiconductor chip / first protective film laminate before the determination has a large S (C) / S (Sn) value to such an extent that it is not determined to be the semiconductor chip with the first protective film, for example, FIG.
  • the same configuration as that in which the amount of the first protective film residue on the bump is further increased is provided.
  • Polymer component (A) Polymer component (A) -1: polyvinyl butyral having structural units represented by the following formulas (i) -1, (i) -2 and (i) -3 ("S-Lec BL-10" manufactured by Sekisui Chemical Co., Ltd.) , Weight average molecular weight 25,000, glass transition temperature 59 ° C)
  • l 1 is about 28, m 1 is 1 to 3, and n 1 is an integer of 68 to 74.
  • Epoxy resin (B1) -1 Liquid bisphenol A type epoxy resin (manufactured by DIC "EPICLON EXA-4810-1000", weight average molecular weight 4300, epoxy equivalent 408 g / eq)
  • Epoxy resin (B1) -2 dicyclopentadiene type epoxy resin ("EPICLON HP-7200" manufactured by DIC, molecular weight 550, epoxy equivalent 254 to 264 g / eq) ⁇ Heat curing agent (B2) Thermosetting agent (B2) -1: Novolak-type phenol resin ("Shonol (registered trademark) BRG-556" manufactured by Showa Denko KK) ⁇ Hardening accelerator (C) Hardening accelerator (C) -1: 2-phenyl-4,5-dihydroxymethylimidazole ("Cuazole 2PHZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.) ⁇ Filler (D) Filler (D) -1: Sp
  • Example 1 Production of Sheet for Forming First Protective Film >> ⁇ Production of Composition for Forming Thermosetting Resin Film> Polymer component (A) -1 (9.9 parts by mass), epoxy resin (B1) -1 (37.8 parts by mass), epoxy resin (B1) -2 (25.0 parts by mass), thermosetting agent ( B2) -1 (18.1 parts by mass), curing accelerator (C) -1 (0.2 parts by mass) and filler (D) -1 (9.0 parts by mass) are dissolved or dispersed in methyl ethyl ketone By stirring at 23 ° C., a composition for forming a resin layer (III) having a solid content concentration of 55% by mass was obtained as a composition for forming a thermosetting resin film.
  • the compounding quantity of each component shown here is all solid content.
  • thermosetting resin film obtained above is used on the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Corporation, 38 ⁇ m thick) obtained by release treatment of one side of a polyethylene terephthalate film by silicone treatment.
  • the composition for formation was applied and dried by heating at 120 ° C. for 2 minutes to form a thermosetting resin film with a thickness of 30 ⁇ m.
  • thermosetting resin film on the above-mentioned release film is bonded to the sticking target layer of the sticking tape to obtain the first A support sheet, a thermosetting resin film, and a release film were laminated in this thickness direction in this order, to obtain a first protective film-forming sheet having a structure shown in FIG.
  • the shape of the bumps is generally spherical as shown in FIG. 1, the height of the bumps is 210 ⁇ m, the width of the bumps is 250 ⁇ m, and the distance between adjacent bumps is 400 ⁇ m.
  • the thickness of the removed portion was 780 ⁇ m.
  • the surface (rear surface) opposite to the bump formation surface of the semiconductor wafer in the obtained laminated structure (1) was ground.
  • the back surface was ground until the thickness of the portion excluding the bumps of the semiconductor wafer became 280 ⁇ m.
  • the laminated structure (1) after grinding the back surface under the conditions of illuminance 230 mW / cm 2 and light quantity 570 mJ / cm 2
  • the first protective film forming sheet was irradiated with ultraviolet light.
  • the layer in contact with the thermosetting resin film in the first support sheet in the first protective film-forming sheet was cured by ultraviolet light.
  • the first support sheet (sticking sheet) was peeled from the thermosetting resin film in the laminated structure (1) using a sticking apparatus (“RAD-2700 F / 12” manufactured by Lintec Corporation).
  • the laminated structure (2) semiconductor wafer with a curable resin film
  • thermosetting resin film in (2) was thermally cured to form a first protective film.
  • a laminated structure (3) (a semiconductor wafer with a first protective film) including the first protective film provided on the bump formation surface of the semiconductor wafer was obtained.
  • plasma is applied to the bump upper portion of the semiconductor wafer in the laminated structure (3) obtained above using a plasma irradiator (“RIE-10 NRT” manufactured by samco), and An operation to reduce the amount of the first protective film residue was performed.
  • the plasma was irradiated for 1 minute by setting the flow rate of tetrafluoromethane (CF 4 ) gas to 40 sccm, the flow rate of oxygen gas to 80 sccm, an output of 250 W, and a pressure of 100 Pa after gas introduction.
  • CF 4 tetrafluoromethane
  • a dicing tape ("Adwill D-675" manufactured by Lintec Corporation) is attached to the back surface (ground surface) of the semiconductor wafer in the obtained laminated structure (4) to form a bump-formed surface of the semiconductor wafer
  • a laminated structure (5) was obtained, which was provided with the first protective film and the dicing tape on the back surface.
  • the semiconductor wafer in the laminated structure (5) is singulated together with the first protective film (Ie, the laminated structure (4) was singulated) to form a semiconductor chip having a size of 6 mm ⁇ 6 mm to obtain a laminated structure (6).
  • the semiconductor chip / first protective film laminate configured to include the first protective film on the bump formation surface of the semiconductor chip was separated from the dicing tape after the ultraviolet irradiation and picked up.
  • FIG. 11 is a plan view for explaining the arrangement position on the dicing tape of the semiconductor chip-first protective film laminate to be analyzed. As shown in FIG. 11, 144 semiconductor chip / first protective film laminates 1 ′ are disposed on the dicing tape 8.
  • EDX analysis was performed on six semiconductor chip / first protective film laminates 1 ′ denoted by reference numerals 1′-1 to 1′-6.
  • EDX analysis was performed on the upper area including the top of the bump.
  • the upper area is an area recognized as a circular area including the top of the bump and having a diameter of 100 ⁇ m when the bump is viewed from above and viewed in plan from above. That is, this circular area was made into the scanning range in EDX.
  • the average value of the obtained S (C) / S (Sn) values was adopted as the S (C) / S (Sn) value in this example.
  • the semiconductor chip / first protective film laminate after pickup obtained above is placed on the surface of a substrate (KIT WLP (s) 300 P / 400 P, thickness 1000 ⁇ m) coated with flux, and it is at 350 ° C.
  • the substrate was bonded by heating for 2 minutes. At this time, the bumps in the semiconductor chip-first protective film laminate were in contact with the surface of the substrate. The substrate was then cleaned to remove the flux. Next, a resistance value between the semiconductor chip and the substrate was measured using a tester (“3422 HiCARDTESTER” manufactured by HIOKI).
  • Example 2 Production of Sheet for Forming First Protective Film >> In the same manner as in Example 1, a sheet for forming a first protective film was produced.
  • a dicing tape ("Adwill D-675" manufactured by Lintec Corporation) is attached to the back surface (grind surface) of the semiconductor wafer in the obtained laminated structure (3) to form a bump-formed surface of the semiconductor wafer A laminated structure (7) was obtained, which was provided with the first protective film and the dicing tape on the back surface.
  • the bumps were processed under conditions of a blade rotational speed of 30,000 rpm and a blade feed speed of 50 mm / s. At a portion 50 ⁇ m below the apex, cutting was performed in a direction parallel to the bump formation surface to remove a cut piece.
  • the bump has a height of 160 ⁇ m and the head is flat except for the example 1
  • the shape of the bumps is as shown in FIG.
  • the obtained laminated structure (8) was further washed using the washing unit of the dicing apparatus.
  • a laminated structure (9) was obtained by singulating together with 1 protective film and forming a semiconductor chip having a size of 6 mm ⁇ 6 mm.
  • the dicing tape in the laminated structure (9) was irradiated with ultraviolet light using the laminated structure (9) obtained above in place of the laminated structure (6) described above. Thereby, the layer in contact with the semiconductor chip in the dicing tape was cured by ultraviolet light.
  • the semiconductor chip / first protective film laminate configured to have the first protective film on the bump formed surface of the semiconductor chip is separated from the dicing tape after the ultraviolet irradiation. I picked it up.
  • the semiconductor in the laminated structure (1R) is the same method as in Example 1 except that the laminated structure (1R) obtained above is used instead of the above-mentioned laminated structure (1)
  • the backside of the wafer was ground until the thickness of the portion excluding the bumps was 280 ⁇ m.
  • a dicing tape (“Adwill D-675” manufactured by Lintec Corporation) was attached to the back surface (ground surface) of the semiconductor wafer to obtain a laminated structure (2R).
  • Example 2 In the same manner as in Example 1, except that the above-described laminated structure (4R) was used instead of the above-described laminated structure (6), the conditions in the laminated structure (4R) were used.
  • the dicing tape was irradiated with ultraviolet light. Thereby, the layer in contact with the semiconductor chip in the dicing tape was cured by ultraviolet light.
  • the semiconductor chip was separated from the dicing tape after ultraviolet irradiation and picked up.
  • Comparative Example 2 In the same manner as in Example 1, a sheet for forming a first protective film was produced. Then, in the same manner as in Example 1, except that the time for irradiating plasma to the bump upper portion of the semiconductor wafer in the laminated structure (3) is changed to 1 minute instead of 1 minute, A semiconductor chip / first protective film laminate was manufactured, and bumps were evaluated. The results are shown in Table 1.
  • the S (C) / S (Sn) value is 0.24 or less (0.07 to 0.24).
  • the amount of the first protective film residue was small at the top of the bump. This is because the residue reduction step is performed in Example 1 by irradiating plasma on the bumps of the semiconductor wafer for one minute in the production of the semiconductor chip / first protective film laminate, and in Example 2, The reason is that the residue reduction process is performed by removing the upper part of the bump.
  • the bonding strength between the copper plate and the bump was high, and the shear failure in the bonded body of the copper plate and the semiconductor chip was cohesive failure (breaking of the bump).
  • the degree of electrical connection in the joined body of the substrate and the semiconductor chip was also high.
  • the semiconductor chip / first protective film laminate manufactured in Examples 1 and 2 is the target semiconductor chip with a first protective film.
  • the first protective film is not provided, there is no factor that the S (C) / S (Sn) value becomes high, and in fact S (C) / S (Sn) The value was low.
  • the evaluation results described above in Examples 1 and 2, particularly in Example 2, are on the same level as the evaluation results in Reference Example 1.
  • the first protective film residue at the top of the bump is It was judged that the reduction effect of the amount was high.
  • the S (C) / S (Sn) value is 0.33, and the amount of the first protective film residue is large at the top of the bump.
  • the irradiation time of plasma to the bump upper portion of the semiconductor wafer is short, and the reduction of the amount of the first protective film residue on the bump upper portion is insufficient. is there.
  • the bond strength between the copper plate and the bump was high reflecting such results, the degree of electrical connection in the bonded body of the substrate and the semiconductor chip was low.
  • the present invention can be used to manufacture a semiconductor chip or the like having bumps in the connection pad portion, which is used in flip chip mounting.

Abstract

A semiconductor chip with a first protective film according to the present embodiment is provided with: a semiconductor chip; and a first protective film formed on a bump-containing surface of the semiconductor chip, wherein, when analyzing the top of the bumps by energy dispersive X-ray spectroscopy to measure the intensity S(C) of the detection signal of carbon and the intensity S(Sn) of the detection signal of tin, the value of S(C)/S(Sn) is 0.32 or less.

Description

第１保護膜付き半導体チップ、第１保護膜付き半導体チップの製造方法、及び半導体チップ・第１保護膜積層体の評価方法First protective film-provided semiconductor chip, method of manufacturing semiconductor chip with first protective film, and method of evaluating semiconductor chip / first protective film laminate
　本発明は、第１保護膜付き半導体チップ、第１保護膜付き半導体チップの製造方法、及び半導体チップ・第１保護膜積層体の評価方法に関する。
　本願は、２０１７年１１月１７日に、日本に出願された特願２０１７－２２１９８５号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a semiconductor chip with a first protective film, a method of manufacturing a semiconductor chip with a first protective film, and a method of evaluating a semiconductor chip / first protective film laminate.
Priority is claimed on Japanese Patent Application No. 2017-221985, filed Nov. 17, 2017, the content of which is incorporated herein by reference.
　従来、ＭＰＵやゲートアレー等に用いる多ピンのＬＳＩパッケージをプリント配線基板に実装する場合には、半導体チップとして、その接続パッド部に共晶ハンダ、高温ハンダ、金等からなる凸状電極（以下、本明細書においては「バンプ」と称する）が形成されたものを用い、所謂フェースダウン方式により、それらのバンプをチップ搭載用基板上の相対応する端子部に対面、接触させ、溶融／拡散接合するフリップチップ実装方法が採用されてきた。 Conventionally, when mounting a multi-pin LSI package used for an MPU, gate array, etc. on a printed wiring board, a convex electrode (hereinafter referred to as a semiconductor chip) made of eutectic solder, high temperature solder, gold etc. In the present specification, using what is referred to as “bumps”, these bumps are made to face and contact corresponding terminal portions on the chip mounting substrate by the so-called face-down method, and melting / diffusion A flip chip mounting method to bond has been employed.
　この実装方法で用いる半導体チップは、例えば、回路面にバンプが形成された半導体ウエハの、回路面（換言するとバンプ形成面）とは反対側の面を研削したり、半導体ウエハをダイシングして個片化することにより得られる。このような半導体チップを得る過程においては、通常、半導体ウエハのバンプ形成面及びバンプを保護する目的で、硬化性樹脂フィルムをバンプ形成面に貼付し、このフィルムを硬化させて、バンプ形成面に保護膜を形成する。 The semiconductor chip used in this mounting method is, for example, a semiconductor wafer having bumps formed on the circuit surface, and the surface on the opposite side to the circuit surface (in other words, the bump formation surface) is ground or the semiconductor wafer is diced. It is obtained by fragmenting. In the process of obtaining such a semiconductor chip, usually, for the purpose of protecting the bump formed surface and the bumps of the semiconductor wafer, a curable resin film is attached to the bump formed surface, and this film is cured to form the bump formed surface. Form a protective film.
　硬化性樹脂フィルムは、通常、加熱により軟化した状態で、半導体ウエハのバンプ形成面に貼付される。このようにすることにより、バンプの頭頂部を含む上部は、硬化性樹脂フィルムを貫通して、硬化性樹脂フィルムから突出する。その一方で、硬化性樹脂フィルムは、半導体ウエハのバンプを覆うようにしてバンプ間に広がり、バンプ形成面に密着するとともに、バンプの表面、特にバンプ形成面の近傍部位の表面を覆って、バンプを埋め込む。この後、硬化性樹脂フィルムは、さらに硬化によって、半導体ウエハのバンプ形成面と、バンプのバンプ形成面の近傍部位の表面と、を被覆して、これらの領域を保護する保護膜となる。さらに、半導体ウエハは、半導体チップに個片化され、最終的に、バンプ形成面に保護膜を備えた半導体チップ（本明細書においては、「保護膜付き半導体チップ」と称することがある）となる。 The curable resin film is usually attached to the bump formation surface of the semiconductor wafer in a softened state by heating. By doing this, the upper portion including the top of the bump penetrates the curable resin film and protrudes from the curable resin film. On the other hand, the curable resin film spreads between the bumps so as to cover the bumps of the semiconductor wafer and adheres to the bump formation surface, and covers the surface of the bumps, particularly the surface near the bump formation surface. Embed After that, the curable resin film is further cured to cover the bump formation surface of the semiconductor wafer and the surface of the vicinity of the bump formation surface of the bump, to form a protective film for protecting these regions. Furthermore, the semiconductor wafer is singulated into semiconductor chips, and finally, a semiconductor chip provided with a protective film on the bump formation surface (sometimes referred to as “semiconductor chip with protective film” in the present specification) Become.
　このような保護膜付き半導体チップは、基板上に搭載されて半導体パッケージとなり、さらにこの半導体パッケージを用いて、目的とする半導体装置が構成される。半導体パッケージ及び半導体装置が正常に機能するためには、保護膜付き半導体チップのバンプと、基板上の回路と、の電気的接続が阻害されないことが必要である。ところが、硬化性樹脂フィルムが、半導体ウエハのバンプ形成面に対して適切に貼付されなければ、バンプの硬化性樹脂フィルムからの突出が不十分となったり、バンプの頭頂部に硬化性樹脂フィルムの一部が残存したりしてしまう。このようにバンプの頭頂部に残存した硬化性樹脂フィルムは、他の領域の硬化性樹脂フィルムの場合と同様に硬化して、保護膜と同様の組成を有する硬化物（本明細書においては、「保護膜残留物」と称することがある）となる。すると、バンプの頭頂部は、バンプと基板上の回路との電気的接続領域であるため、保護膜残留物の量が多い場合には、保護膜付き半導体チップのバンプと、基板上の回路と、の電気的接続が阻害されてしまう。
　すなわち、保護膜付き半導体チップの基板上への搭載前の段階で、保護膜付き半導体チップのバンプの頭頂部においては、保護膜残留物が存在しないか、又は保護膜残留物の量が少ないことが求められる。 Such a semiconductor chip with a protective film is mounted on a substrate to be a semiconductor package, and the semiconductor package is used to form a target semiconductor device. In order for the semiconductor package and the semiconductor device to function properly, it is necessary that the electrical connection between the bump of the semiconductor chip with a protective film and the circuit on the substrate is not inhibited. However, if the curable resin film is not appropriately attached to the bump formation surface of the semiconductor wafer, the protrusion of the bump from the curable resin film may be insufficient, or the curable resin film may be formed on the top of the bump. Some will survive. Thus, the curable resin film remaining on the top of the bumps is cured as in the case of the curable resin film in the other regions, and a cured product having a composition similar to that of the protective film (herein, It may be called "protective film residue". Then, since the top of the bump is an electrical connection area between the bump and the circuit on the substrate, the bump on the semiconductor chip with the protective film, and the circuit on the substrate, when the amount of protective film residue is large. , The electrical connection of will be blocked.
That is, at the stage before mounting the semiconductor chip with a protective film on the substrate, at the top of the bump of the semiconductor chip with a protective film, there is no protective film residue or the amount of protective film residue is small. Is required.
　このように、バンプの頭頂部において、保護膜残留物の残存を抑制できるとされている方法としては、重量平均分子量が２万～１００万の高分子量成分と、熱硬化性樹脂と、硬化促進剤と、光反応性モノマーと、光開始剤と、を含有する硬化性樹脂フィルム（粘接着剤層）を用いる方法が開示されている（特許文献１参照）。 Thus, as a method which is considered to be capable of suppressing the remaining of the protective film residue at the top of the bump, a high molecular weight component having a weight average molecular weight of 20,000 to 1,000,000, a thermosetting resin, and curing acceleration Patent Document 1 discloses a method of using a curable resin film (adhesive / adhesive layer) containing an agent, a photoreactive monomer, and a photoinitiator.
日本国特許第５５１５８１１号公報Japanese Patent No. 5515811
　通常、バンプの表面には、微小な凹凸が多数存在し、バンプの頭頂部に保護膜残留物が存在する場合には、バンプ表面の凹部内に保護膜残留物が侵入している可能性がある。したがって、バンプの頭頂部における保護膜残留物の量の評価は、容易ではない。 Usually, if there are a lot of small irregularities on the surface of the bump, and there is a protective film residue on the top of the bump, there is a possibility that the protective film residue has penetrated into the concave portion of the bump surface is there. Therefore, the evaluation of the amount of protective film residue on the top of the bump is not easy.
　これに対して、特許文献１に記載の方法では、硬化性樹脂フィルム（粘接着剤層）に由来する、バンプの頭頂部における残留物の有無を、目視又は顕微鏡を用いた観察によって評価している。このように、この方法では、バンプの頭頂部における保護膜残留物の量を定量するなど、より高精度な評価は行っておらず、バンプの頭頂部における残留物の残存を実際に抑制できているか定かでなはい、という問題点があった。 On the other hand, in the method described in Patent Document 1, the presence or absence of the residue at the top of the bump derived from the curable resin film (adhesive / adhesive layer) is evaluated by visual observation or observation using a microscope. ing. As described above, in this method, the amount of the protective film residue on the top of the bump is quantified, etc., and more accurate evaluation is not performed, and the remaining of the residue on the top of the bump can be actually suppressed. There was a problem that it was obvious that there was no problem.
　本発明は、バンプの頭頂部において保護膜残留物の残存が抑制されている保護膜付き半導体チップと、前記保護膜付き半導体チップの製造方法と、前記保護膜付き半導体チップであるか否かを高精度に評価できる評価方法と、を提供することを目的とする。 The present invention relates to a semiconductor chip with a protective film in which the remaining of a protective film residue is suppressed at the top of the bump, a method of manufacturing the semiconductor chip with a protective film, and whether it is the semiconductor chip with a protective film. It aims at providing an evaluation method that can be evaluated with high accuracy.
　本発明は、半導体チップと、前記半導体チップのバンプを有する面に形成された第１保護膜と、を備え、前記バンプの頭頂部について、エネルギー分散型Ｘ線分光法によって分析を行い、炭素の検出シグナルの強度Ｓ（Ｃ）と、スズの検出シグナルの強度Ｓ（Ｓｎ）と、を測定したとき、Ｓ（Ｃ）／Ｓ（Ｓｎ）の値が０．３２以下となる、第１保護膜付き半導体チップを提供する。 The present invention comprises a semiconductor chip and a first protective film formed on the surface of the semiconductor chip having a bump, and the top of the bump is analyzed by energy dispersive X-ray spectroscopy to obtain carbon A first protective film in which the value of S (C) / S (Sn) is 0.32 or less when the intensity S (C) of the detection signal and the intensity S (Sn) of the detection signal of tin are measured To provide a semiconductor chip with
　また、本発明は、前記第１保護膜付き半導体チップの製造方法であって、半導体ウエハのバンプを有する面に、硬化性樹脂フィルムを貼付する工程と、貼付後の前記硬化性樹脂フィルムを硬化させることにより、第１保護膜を形成する工程と、前記半導体ウエハを分割することにより、半導体チップを得る工程と、を有し、前記硬化性樹脂フィルムを貼付する工程において、前記Ｓ（Ｃ）／Ｓ（Ｓｎ）の値が０．３２以下となるように、前記バンプの頭頂部を前記硬化性樹脂フィルムから突出させるか、又は、前記硬化性樹脂フィルムを貼付する工程の後に、さらに、前記Ｓ（Ｃ）／Ｓ（Ｓｎ）の値が０．３２以下となるように、前記バンプ上の残留物の量を低減する工程を有する、第１保護膜付き半導体チップの製造方法を提供する。
　また、本発明は、半導体チップと、前記半導体チップのバンプを有する面に形成された第１保護膜と、を備えた、半導体チップ・第１保護膜積層体の評価方法であって、前記半導体チップ・第１保護膜積層体中の前記バンプの頭頂部について、エネルギー分散型Ｘ線分光法によって分析を行い、炭素の検出シグナルの強度Ｓ（Ｃ）と、スズの検出シグナルの強度Ｓ（Ｓｎ）と、を測定し、Ｓ（Ｃ）／Ｓ（Ｓｎ）の値が０．３２以下である場合には、前記半導体チップ・第１保護膜積層体を、目的とする第１保護膜付き半導体チップであると判定し、Ｓ（Ｃ）／Ｓ（Ｓｎ）の値が０．３２よりも大きい場合には、前記半導体チップ・第１保護膜積層体を、目的とする第１保護膜付き半導体チップではないと判定する、半導体チップ・第１保護膜積層体の評価方法を提供する。 Further, the present invention is a method for producing the semiconductor chip with a first protective film, which comprises the steps of attaching a curable resin film to the surface of the semiconductor wafer having bumps, and curing the curable resin film after attachment. Forming a first protective film, and dividing the semiconductor wafer to obtain a semiconductor chip, and attaching the curable resin film, wherein the S (C) is formed. After the step of causing the top of the bump to protrude from the curable resin film or attaching the curable resin film so that the value of / S (Sn) is 0.32 or less A method of manufacturing a semiconductor chip with a first protective film, comprising the step of reducing the amount of residue on the bumps such that the value of S (C) / S (Sn) is 0.32 or less.
Further, according to the present invention, there is provided a method of evaluating a semiconductor chip / first protective film laminate, comprising: a semiconductor chip; and a first protective film formed on a surface of the semiconductor chip having a bump. The top of the bump in the chip / first protective film stack is analyzed by energy dispersive X-ray spectroscopy, and the intensity S (C) of the carbon detection signal and the intensity S (Sn) of the detection signal of tin ), And when the value of S (C) / S (Sn) is 0.32 or less, the semiconductor chip / first protective film laminate is a target semiconductor with a first protective film When it is determined that the chip is a chip, and the value of S (C) / S (Sn) is larger than 0.32, the semiconductor chip / first protective film laminate is used as a target semiconductor with a first protective film Semiconductor chip, first protective film that is judged not to be a chip It provides a method for evaluating lamina.
　本発明の第１保護膜付き半導体チップにおいては、バンプの頭頂部において保護膜残留物の残存が抑制されている。このような第１保護膜付き半導体チップを、基板と接合することで、電気的接続度が高い接合体が得られる。
　本発明の第１保護膜付き半導体チップの製造方法を適用することで、上述の第１保護膜付き半導体チップを製造できる。
　本発明の半導体チップ・第１保護膜積層体の評価方法を適用することで、半導体チップ・第１保護膜積層体が、上述の第１保護膜付き半導体チップであるか否かを高精度に評価できる。 In the semiconductor chip with a first protective film of the present invention, the residual of the protective film residue is suppressed at the top of the bump. By bonding such a semiconductor chip with a first protective film to a substrate, a bonded body having a high degree of electrical connection can be obtained.
By applying the method for manufacturing a semiconductor chip with a first protective film of the present invention, the above-described semiconductor chip with a first protective film can be manufactured.
By applying the evaluation method of the semiconductor chip / first protective film laminate of the present invention, it is possible to accurately determine whether the semiconductor chip / first protective film laminate is the above-described semiconductor chip with a first protective film. It can be evaluated.
本発明の第１保護膜付き半導体チップの一実施形態を模式的に示す拡大断面図である。It is an expanded sectional view showing typically one embodiment of a semiconductor chip with a 1st protective film of the present invention. 本発明の第１保護膜付き半導体チップの他の実施形態を模式的に示す拡大断面図である。It is an expanded sectional view showing typically another embodiment of a semiconductor chip with a 1st protective film of the present invention. 本発明の第１保護膜付き半導体チップのさらに他の実施形態を模式的に示す拡大断面図である。It is an expanded sectional view showing typically another embodiment of a semiconductor chip with a 1st protective film of the present invention. 本発明の第１保護膜付き半導体チップのさらに他の実施形態を模式的に示す拡大断面図である。It is an expanded sectional view showing typically another embodiment of a semiconductor chip with a 1st protective film of the present invention. 本発明の第１保護膜付き半導体チップの製造方法の一実施形態を模式的に説明するための拡大断面図である。It is an expanded sectional view for describing typically an embodiment of a manufacturing method of a semiconductor chip with a 1st protective film of the present invention. 本発明の第１保護膜付き半導体チップの製造方法で用いる、第１保護膜形成用シートの一例を模式的に示す拡大断面図である。It is an expanded sectional view showing typically an example of the sheet for the 1st protective film formation used with the manufacturing method of the semiconductor chip with a 1st protective film of the present invention. 本発明の第１保護膜付き半導体チップの製造方法における、バンプ上の残留物の量を低減する工程の一例を、模式的に説明するための拡大断面図である。It is an expanded sectional view for explaining typically an example of the process of reducing the quantity of the residue on bump in the manufacturing method of the semiconductor chip with a 1st protective film of the present invention. 本発明の第１保護膜付き半導体チップの製造方法における、バンプ上の残留物の量を低減する工程の他の例を、模式的に説明するための拡大断面図である。FIG. 7 is an enlarged cross sectional view for schematically illustrating another example of the step of reducing the amount of residue on bumps in the method of manufacturing a semiconductor chip with a first protective film of the present invention. 本発明の第１保護膜付き半導体チップの製造方法における、バンプ上の残留物の量を低減する工程のさらに他の例を、模式的に説明するための拡大断面図である。FIG. 14 is an enlarged cross sectional view for schematically illustrating still another example of the step of reducing the amount of residue on bumps in the method of manufacturing a semiconductor chip with a first protective film of the present invention. 本発明の第１保護膜付き半導体チップの製造方法における、バンプ上の残留物の量を低減する工程のさらに他の例を、模式的に説明するための拡大断面図である。FIG. 14 is an enlarged cross sectional view for schematically illustrating still another example of the step of reducing the amount of residue on bumps in the method of manufacturing a semiconductor chip with a first protective film of the present invention. 実施例において、バンプの頭頂部についてＥＤＸ分析を行う対象である半導体チップ・第１保護膜積層体の、ダイシングテープ上での配置位置を説明するための平面図である。In an Example, it is a top view for explaining the arrangement position on a dicing tape of the semiconductor chip and the 1st protective film layered product which is the object which performs EDX analysis about the top of a bump.
◇第１保護膜付き半導体チップ
　本発明の第１保護膜付き半導体チップは、半導体チップと、前記半導体チップのバンプを有する面（本明細書においては、「バンプ形成面」と称することがある）に形成された第１保護膜と、を備えており、前記バンプの頭頂部について、エネルギー分散型Ｘ線分光法（Ｅｎｅｒｇｙ　ｄｉｓｐｅｒｓｉｖｅ　Ｘ－ｒａｙ　ｓｐｅｃｔｒｏｍｅｔｒｙ、本明細書においては「ＥＤＸ」と称することがある）によって分析を行い、炭素の検出シグナルの強度Ｓ（Ｃ）と、スズの検出シグナルの強度Ｓ（Ｓｎ）と、を測定したとき、Ｓ（Ｃ）／Ｓ（Ｓｎ）の値（本明細書においては、「Ｓ（Ｃ）／Ｓ（Ｓｎ）値」と略記することがある）が０．３２以下となる。 Semiconductor Chip with First Protective Film The semiconductor chip with a first protective film of the present invention is a semiconductor chip, and a surface having bumps of the semiconductor chip (sometimes referred to as a “bump forming surface” in the present specification) A first protective film formed on the top of the bump, and the top of the bump may be referred to as "energy dispersive X-ray spectrometry (EDX)" in the present specification. When the intensity S (C) of the carbon detection signal and the intensity S (Sn) of the tin detection signal are measured, the value of S (C) / S (Sn) (this specification). In some cases, "S (C) / S (Sn) value" may be abbreviated as 0.32 or less.
　バンプの頭頂部をＥＤＸによって分析したときに、スズ（Ｓｎ）のシグナルが検出されるのは、バンプがその構成材料としてスズを含有するためである。
　その一方で、バンプは、その構成材料として、有機化合物を含有しない。したがって、バンプの頭頂部をＥＤＸによって分析したときに、炭素（Ｃ）のシグナルが検出されるのは、分析領域（すなわちバンプの頭頂部）に、本来は存在しないはずの有機化合物が存在するためである。この有機化合物は、第１保護膜の形成時に用いた硬化性樹脂フィルムに由来する。硬化性樹脂フィルムをバンプ形成面に貼付するときに、バンプの頭頂部に本来は不要な硬化性樹脂フィルムが残留すると、この残留物（本明細書においては、「硬化性樹脂フィルム残留物」と称することがある）が硬化によって、第１保護膜と同様の組成を有する硬化物（本明細書においては、「第１保護膜残留物」と称することがある）となる。この第１保護膜残留物に、上述の有機化合物が含まれる。このような第１保護膜残留物が存在すると、バンプの頭頂部をＥＤＸによって分析したときに、炭素（Ｃ）のシグナルが検出される。なお、本発明の第１保護膜付き半導体チップの製造方法については、後ほど詳しく説明する。 When the top of the bump is analyzed by EDX, the tin (Sn) signal is detected because the bump contains tin as its constituent material.
On the other hand, the bump does not contain an organic compound as its constituent material. Therefore, when the top of the bump is analyzed by EDX, the carbon (C) signal is detected because there is an organic compound which is not originally present in the analysis area (that is, the top of the bump). It is. This organic compound originates in the curable resin film used at the time of formation of the first protective film. When the curable resin film is attached to the bump forming surface, if the originally unnecessary curable resin film remains on the top of the bump, this residue (in this specification, "curable resin film residue" As it cures, it sometimes becomes a cured product having the same composition as the first protective film (sometimes referred to herein as "first protective film residue"). The first protective film residue contains the organic compound described above. When such a first protective film residue is present, a signal of carbon (C) is detected when the top of the bump is analyzed by EDX. The method of manufacturing the semiconductor chip with a first protective film of the present invention will be described in detail later.
　第１保護膜付き半導体チップにおいて、バンプの頭頂部におけるＳ（Ｃ）／Ｓ（Ｓｎ）値は０．３２以下であり、０の場合もある。これは、バンプの頭頂部において、スズの量に対して炭素の量が顕著に少ないことを意味している。すなわち、第１保護膜付き半導体チップは、バンプの頭頂部において、第１保護膜残留物が存在しないか、又は第１保護膜残留物の量が少なく、第１保護膜残留物の残存が抑制されている。このように、バンプの頭頂部において、第１保護膜残留物の残存が抑制されていることにより、第１保護膜付き半導体チップを用いた場合には、そのバンプと基板との間の接合強度が高くなる。また、その半導体チップと基板との接合体における電気的接続度が高くなり、導電性に優れる。 In the semiconductor chip with the first protective film, the S (C) / S (Sn) value at the top of the bump is 0.32 or less, and may be zero. This means that the amount of carbon is significantly lower than the amount of tin at the top of the bump. That is, in the semiconductor chip with the first protective film, the first protective film residue does not exist or the amount of the first protective film residue is small at the top of the bump, and the residual of the first protective film residue is suppressed It is done. Thus, when the semiconductor chip with the first protective film is used by suppressing the remaining of the first protective film residue at the top of the bump, the bonding strength between the bump and the substrate is obtained. Becomes higher. In addition, the degree of electrical connection in the joined body of the semiconductor chip and the substrate is high, and the conductivity is excellent.
　なお、本明細書において、「バンプの頭頂部において、第１保護膜残留物の量が少ない」とは、特に断りのない限り、バンプの頭頂部に第１保護膜残留物が僅かに残存しているものの、その残存量が、このバンプを備えた半導体チップを配線基板にフリップチップ実装したときに、半導体チップと配線基板との電気的接続を妨げない程度であること、を意味する。
　また、半導体ウエハのバンプ形成面とは反対側の面を「裏面」と称することがある。 In the present specification, “the amount of the first protective film residue is small at the top of the bump” means that the first protective film remains slightly at the top of the bump unless otherwise specified. However, this means that the remaining amount is such that it does not prevent the electrical connection between the semiconductor chip and the wiring substrate when the semiconductor chip having the bumps is flip-chip mounted on the wiring substrate.
Moreover, the surface on the opposite side to the bump formation surface of a semiconductor wafer may be called a "back surface."
　第１保護膜付き半導体チップ中のバンプの表面には、微小な凹凸が多数存在し、バンプの頭頂部に第１保護膜残留物が存在する場合には、バンプ表面の凹部内に第１保護膜残留物が侵入している可能性がある。このような凹部内の第１保護膜残留物は、視覚的な方法では確認と定量が難しく、第１保護膜残留物の量が少ない場合には、特にその傾向が強い。これに対して、本発明の第１保護膜付き半導体チップにおいては、バンプの頭頂部における第１保護膜残留物の残存の程度が、ＥＤＸでの分析結果に基づいて精密に特定されている。したがって、本発明の第１保護膜付き半導体チップは、第１保護膜残留物の量の点において、極めて信頼性が高い。 In the case where a large number of minute irregularities exist on the surface of the bump in the semiconductor chip with the first protective film, and the first protective film residue is present on the top of the bump, the first protection is in the concave portion of the bump surface. It is possible that membrane residue has penetrated. The first protective film residue in such a recess is difficult to confirm and quantify by visual methods, and is particularly strong when the amount of the first protective film residue is small. On the other hand, in the semiconductor chip with a first protective film of the present invention, the degree of remaining of the first protective film residue at the top of the bump is precisely specified based on the analysis result by EDX. Therefore, the semiconductor chip with a first protective film of the present invention is extremely reliable in terms of the amount of the first protective film residue.
　第１保護膜付き半導体チップにおいて、バンプの頭頂部におけるＳ（Ｃ）／Ｓ（Ｓｎ）値は、０．３２以下であり、０．３以下であることが好ましく、０．２８以下であることがより好ましく、０．２６以下であることがさらに好ましく、例えば、０．２以下、０．１５以下及び０．１以下等のいずれかであってもよい。Ｓ（Ｃ）／Ｓ（Ｓｎ）値が前記上限値以下であることで、バンプの頭頂部において、第１保護膜残留物の残存がより抑制されているため、第１保護膜付き半導体チップが奏する本発明の効果がより顕著となる。 In the semiconductor chip with the first protective film, the S (C) / S (Sn) value at the top of the bump is 0.32 or less, preferably 0.3 or less, and 0.28 or less Is more preferably 0.26 or less, and may be 0.2 or less, 0.15 or less, or 0.1 or less, for example. When the S (C) / S (Sn) value is less than or equal to the upper limit value, the residual of the first protective film residue is further suppressed at the top of the bump, so that the semiconductor chip with the first protective film The effect of the present invention to play is more remarkable.
　第１保護膜付き半導体チップにおいて、バンプの頭頂部におけるＳ（Ｃ）／Ｓ（Ｓｎ）値の下限値は、０以上であれば特に限定されない。例えば、Ｓ（Ｃ）／Ｓ（Ｓｎ）値は、０．０３以上であってもよく、このような第１保護膜付き半導体チップは、より容易に製造できる。 In the semiconductor chip with a first protective film, the lower limit value of the S (C) / S (Sn) value at the top of the bump is not particularly limited as long as it is 0 or more. For example, the S (C) / S (Sn) value may be 0.03 or more, and such a semiconductor chip with a first protective film can be manufactured more easily.
　第１保護膜付き半導体チップにおいて、バンプの頭頂部におけるＳ（Ｃ）／Ｓ（Ｓｎ）値は、上述のいずれかの下限値及び上限値を任意に組み合わせて設定される範囲内となるように、適宜調節できる。
　例えば、一実施形態において、Ｓ（Ｃ）／Ｓ（Ｓｎ）値は、好ましくは０～０．３２、より好ましくは０～０．３、さらに好ましくは０～０．２８、特に好ましくは０～０．２６であり、例えば、０～０．２、０～０．１５、及び０～０．１等のいずれかであってもよい。また、一実施形態において、Ｓ（Ｃ）／Ｓ（Ｓｎ）値は、好ましくは０．０３～０．３２、より好ましくは０．０３～０．３、さらに好ましくは０．０３～０．２８、特に好ましくは０．０３～０．２６であり、例えば、０．０３～０．２、０．０３～０．１５、及び０．０３～０．１等のいずれかであってもよい。ただし、これらは、Ｓ（Ｃ）／Ｓ（Ｓｎ）値の一例である。 In the semiconductor chip with the first protective film, the S (C) / S (Sn) value at the top of the bump is within the range set by any combination of the lower limit and the upper limit described above. , Can be adjusted accordingly.
For example, in one embodiment, the S (C) / S (Sn) value is preferably 0 to 0.32, more preferably 0 to 0.3, still more preferably 0 to 0.28, particularly preferably 0 to It may be 0.26, for example, any of 0 to 0.2, 0 to 0.15, and 0 to 0.1 or the like. In one embodiment, the S (C) / S (Sn) value is preferably 0.03 to 0.32, more preferably 0.03 to 0.3, and still more preferably 0.03 to 0.28. And particularly preferably 0.03 to 0.26, and may be, for example, 0.03 to 0.2, 0.03 to 0.15, and 0.03 to 0.1 or the like. However, these are examples of S (C) / S (Sn) values.
　ＥＤＸ分析を行うバンプの頭頂部とは、バンプの頂上を含む上部領域を意味する。前記頭頂部としては、例えば、バンプをその上方から見下ろして平面視したときに、バンプの頂上を含み、かつ、直径が好ましくは８０～１２０μｍ、より好ましくは９０～１１０μｍであり、例えば１００μｍ等である円形領域、として認識される領域が挙げられる。このような領域が、ＥＤＸでの走査範囲となる。前記直径が前記下限値以上であることで、ＥＤＸ分析をより高精度に行うことができる。前記直径が前記上限値以下であることで、ＥＤＸ分析をより高効率で行うことができる。
　バンプの前記上部領域の面が曲面である場合には、バンプの頂上として、半導体チップのバンプ形成面からの高さが最も高い位置を選択できる。一方、バンプの前記上部領域の面が平面である場合には、バンプの頂上として、例えば、その平面の中心（重心）を選択できる。
　バンプの形状については、後ほど詳しく説明する。 The top of the bump where EDX analysis is performed means the upper area including the top of the bump. The top of the head includes, for example, the top of the bump when the bump is viewed from above and viewed from above, and the diameter is preferably 80 to 120 μm, more preferably 90 to 110 μm, for example 100 μm An area recognized as a circular area may be mentioned. Such a region is a scanning range in EDX. When the diameter is equal to or more than the lower limit value, EDX analysis can be performed with higher accuracy. When the diameter is equal to or less than the upper limit value, EDX analysis can be performed with higher efficiency.
When the surface of the upper region of the bump is a curved surface, the highest position from the bump formation surface of the semiconductor chip can be selected as the top of the bump. On the other hand, when the surface of the upper region of the bump is a plane, for example, the center (center of gravity) of the plane can be selected as the top of the bump.
The shape of the bumps will be described in detail later.
　ＥＤＸでの分析条件は、特に限定されない。ただし、通常は、加速電圧は１５～３０ｋＶであることが好ましく、レンズ－試料間距離は１０～１５ｍｍであることが好ましい。このような条件とすることで、より高精度に分析できる。 The analysis conditions in EDX are not particularly limited. However, usually, the acceleration voltage is preferably 15 to 30 kV, and the distance between the lens and the sample is preferably 10 to 15 mm. Under such conditions, analysis can be performed with higher accuracy.
　図１は、本発明の第１保護膜付き半導体チップの一実施形態を模式的に示す拡大断面図である。なお、以下の説明で用いる図は、本発明の特徴を分かり易くするために、便宜上、要部となる部分を拡大して示している場合があり、各構成要素の寸法比率等が実際と同じであるとは限らない。 FIG. 1 is an enlarged cross-sectional view schematically showing an embodiment of a semiconductor chip with a first protective film of the present invention. Note that the drawings used in the following description may be enlarged for convenience, in order to make the features of the present invention intelligible. Not necessarily.
　ここに示す第１保護膜付き半導体チップ１は、半導体チップ９と、半導体チップ９のバンプを有する面（バンプ形成面）９ａに形成された第１保護膜１３と、を備えている。
　第１保護膜付き半導体チップ１において、第１保護膜１３は、バンプ形成面９ａに密着するとともに、バンプ９１の表面９１ａ、特にバンプ形成面９ａの近傍部位の表面９１ａを覆って、バンプ９１を埋め込み、これらの領域を保護している。
　図１中、符号９ｂは、半導体チップ９のバンプ形成面９ａとは反対側の面（裏面）を示す。 The semiconductor chip 1 with a first protective film shown here includes a semiconductor chip 9 and a first protective film 13 formed on a surface (bump formation surface) 9 a having bumps of the semiconductor chip 9.
In the semiconductor chip 1 with a first protective film, the first protective film 13 is in close contact with the bump forming surface 9a and covers the surface 91a of the bump 91, particularly the surface 91a in the vicinity of the bump forming surface 9a. Embed and protect these areas.
In FIG. 1, reference numeral 9 b denotes a surface (rear surface) opposite to the bump forming surface 9 a of the semiconductor chip 9.
　バンプ９１の頭頂部９１０は、第１保護膜１３を貫通して、突出している。さらに、バンプ９１の頭頂部９１０には、第１保護膜残留物が存在しない。したがって、バンプ９１の頭頂部９１０について、ＥＤＸ分析を行ったとき、Ｓ（Ｃ）／Ｓ（Ｓｎ）値は０．３２以下と、低水準となる。 The top portions 910 of the bumps 91 protrude through the first protective film 13. Furthermore, the top portion 910 of the bump 91 is free of the first protective film residue. Therefore, when EDX analysis is performed on the top of the bumps 91 of the bumps 91, the S (C) / S (Sn) value becomes as low as 0.32 or less.
　バンプ９１は、球の一部が平面によって切り取られた形状を有しており、その切り取られて露出した部位に相当する平面が、半導体チップ９のバンプ形成面（回路面）９ａに接触した状態となっている。
　バンプ９１の形状は、概ね球状であるといえる。
　バンプ９１の頭頂部９１０は、球面の一部であるといえ、曲面となっている。 The bump 91 has a shape in which a part of the sphere is cut off by a plane, and the plane corresponding to the cut and exposed portion is in contact with the bump forming surface (circuit surface) 9 a of the semiconductor chip 9 It has become.
The shape of the bumps 91 can be said to be generally spherical.
The top portion 910 of the bump 91 is a curved surface although it is part of a spherical surface.
　バンプ９１の高さは特に限定されないが、６０～４５０μｍであることが好ましく、１２０～３００μｍであることがより好ましく、１８０～２４０μｍであることが特に好ましい。バンプ９１の高さが前記下限値以上であることで、バンプ９１の機能をより向上させることができる。また、バンプ９１の高さが前記上限値以下であることで、バンプ９１の頭頂部９１０における、第１保護膜残留物の残存を抑制する効果がより高くなる。
　なお、本明細書において、「バンプの高さ」とは、バンプのうち、バンプ形成面から最も高い位置に存在する部位（頂上）での高さを意味する。 The height of the bumps 91 is not particularly limited, but is preferably 60 to 450 μm, more preferably 120 to 300 μm, and particularly preferably 180 to 240 μm. When the height of the bump 91 is equal to or more than the lower limit value, the function of the bump 91 can be further improved. In addition, when the height of the bumps 91 is equal to or less than the upper limit value, the effect of suppressing the remaining of the first protective film residue in the top portion 910 of the bumps 91 becomes higher.
In the present specification, “the height of the bump” means the height at the portion (the top) of the bump which is at the highest position from the bump formation surface.
　バンプ９１の幅は特に限定されないが、１７０～３５０μｍであることが好ましく、２００～３２０μｍであることがより好ましく、２３０～２９０μｍであることが特に好ましい。バンプ９１の幅が前記下限値以上であることで、バンプ９１の機能をより向上させることができる。また、バンプ９１の幅が前記上限値以下であることで、バンプ９１の頭頂部９１０における、第１保護膜残留物の残存を抑制する効果がより高くなる。
　なお、本明細書において、「バンプの幅」とは、バンプ形成面に対して垂直な方向からバンプを見下ろして平面視したときに、バンプ表面上の異なる２点間を直線で結んで得られる線分の最大値を意味する。 The width of the bumps 91 is not particularly limited, but is preferably 170 to 350 μm, more preferably 200 to 320 μm, and particularly preferably 230 to 290 μm. When the width of the bump 91 is equal to or more than the lower limit value, the function of the bump 91 can be further improved. In addition, when the width of the bump 91 is equal to or less than the upper limit value, the effect of suppressing the remaining of the first protective film residue in the top portion 910 of the bump 91 is further enhanced.
In the present specification, the “bump width” can be obtained by connecting two different points on the surface of the bump with a straight line when the bump is viewed from below in a direction perpendicular to the surface on which the bump is formed. It means the maximum value of the line segment.
　隣り合うバンプ９１間の距離は、特に限定されないが、８０～１０００μｍであることが好ましく、１００～８００μｍであることがより好ましく、１２０～５５０μｍであることが特に好ましい。前記距離が前記下限値以上であることで、バンプ９１の機能をより向上させることができる。また、前記距離が前記上限値以下であることで、バンプ９１の頭頂部９１０における、第１保護膜残留物の残存を抑制する効果がより高くなる。
　なお、本明細書において、「隣り合うバンプ間の距離」とは、隣り合うバンプ同士の中心部間の距離を意味し、「バンプピッチ」と呼ばれることもある。 The distance between adjacent bumps 91 is not particularly limited, but is preferably 80 to 1000 μm, more preferably 100 to 800 μm, and particularly preferably 120 to 550 μm. The function of the bump 91 can be further improved by the distance being equal to or more than the lower limit value. In addition, when the distance is equal to or less than the upper limit value, the effect of suppressing the remaining of the first protective film residue in the top portion 910 of the bump 91 is further enhanced.
In the present specification, "the distance between adjacent bumps" means the distance between the central portions of adjacent bumps, and may be referred to as "bump pitch".
　ここでは、第１保護膜付き半導体チップとして、バンプの頭頂部に、第１保護膜残留物が存在しないものについて示しているが、本発明の第１保護膜付き半導体チップは、バンプの頭頂部に、第１保護膜残留物が少量存在したものであってもよい。このときの第１保護膜残留物の量は、上述のように少なければよい。 Here, although the semiconductor chip with a first protective film is shown for the one in which the first protective film residue is not present on the top of the bump, the semiconductor chip with a first protective film of the present invention is the top of the bump. In addition, a small amount of the first protective film residue may be present. The amount of the first protective film residue at this time may be small as described above.
　図２は、このような本発明の第１保護膜付き半導体チップの一実施形態を模式的に示す拡大断面図である。なお、図２以降の図において、既に説明済みの図に示すものと同じ構成要素には、その説明済みの図の場合と同じ符号を付し、その詳細な説明は省略する。
　ここに示す第１保護膜付き半導体チップ２は、バンプ９１の頭頂部９１０に、第１保護膜残留物１３１が少量存在している点以外は、図１に示す第１保護膜付き半導体チップ１と同じである。 FIG. 2 is an enlarged sectional view schematically showing an embodiment of such a semiconductor chip with a first protective film of the present invention. In the drawings after FIG. 2, the same components as those shown in the already described drawings are denoted by the same reference numerals as in the already explained drawings, and the detailed description thereof will be omitted.
The semiconductor chip with a first protective film 2 shown here is the semiconductor chip with a first protective film 1 shown in FIG. 1 except that a small amount of the first protective film residue 131 is present on the top portion 910 of the bump 91. Is the same as
　第１保護膜付き半導体チップ２は、第１保護膜残留物１３１が残存しているものの、バンプ９１の頭頂部９１０は、第１保護膜１３を貫通して、突出している。
　第１保護膜付き半導体チップ２は、バンプ９１の頭頂部９１０において、第１保護膜残留物１３１の量が少なく、第１保護膜残留物１３１の残存が抑制されている。したがって、バンプ９１の頭頂部９１０について、ＥＤＸ分析を行ったとき、Ｓ（Ｃ）／Ｓ（Ｓｎ）値は０．３２以下と、低水準となる。 Although the first protective film residue 131 remains in the semiconductor chip 2 with a first protective film, the top portion 910 of the bump 91 penetrates the first protective film 13 and protrudes.
In the first protective film-provided semiconductor chip 2, the amount of the first protective film residue 131 is small at the top portion 910 of the bump 91, and the residual of the first protective film residue 131 is suppressed. Therefore, when EDX analysis is performed on the top of the bumps 91 of the bumps 91, the S (C) / S (Sn) value becomes as low as 0.32 or less.
　第１保護膜付き半導体チップ２においては、第１保護膜残留物１３１が、バンプ９１の頭頂部９１０のうち、頂上をほぼ中心として、バンプ９１の表面９１ａの狭い領域に広がって存在している場合を示している。ただし、第１保護膜残留物１３１が存在する場合のその存在領域は、これに限定されず、例えば、バンプ９１の頂上又はその近傍を中心としていなくてもよい。なお、本明細書において、「バンプの頂上（バンプの頭頂部中の頂上）」とは、バンプの表面のうち、半導体チップのバンプ形成面からの高さが最も高い箇所を意味する。 In the first protective film-provided semiconductor chip 2, the first protective film residue 131 is present in a narrow region of the surface 91 a of the bump 91, with the top of the top portion 910 of the bump 91 substantially centered on the top. The case is shown. However, the region where the first protective film residue 131 is present is not limited to this, and may not be centered on the top of the bump 91 or in the vicinity thereof, for example. In the present specification, “the top of the bump (the top in the top of the bump)” means a portion of the surface of the bump that is the highest in height from the surface on which the semiconductor chip is formed.
　ここまでは、第１保護膜付き半導体チップとして、バンプが概ね球状であるものについて説明したが、本発明の第１保護膜付き半導体チップにおいて、バンプの形状はこれに限定されない。 So far, as the semiconductor chip with the first protective film, the one in which the bumps are approximately spherical has been described, but in the semiconductor chip with the first protective film of the present invention, the shape of the bumps is not limited thereto.
　図３は、本発明の第１保護膜付き半導体チップのうち、バンプの形状が概ね球状ではない場合の一実施形態を模式的に示す拡大断面図である。
　ここに示す第１保護膜付き半導体チップ３は、バンプ９１に代えてバンプ９２を備える（すなわち、バンプの形状が異なる）点以外は、図１に示す第１保護膜付き半導体チップ１と同じである。
　より具体的には、バンプ９２は、図１に示すバンプ９１において、頭頂部９１０が曲面ではなく、平面となったものである。すなわち、バンプ９２の頭頂部９２０は平面である。
　なお、図３中、符号９２ａは、バンプ９２のうち、頭頂部９２０以外の領域の表面を示す。 FIG. 3 is an enlarged cross-sectional view schematically showing an embodiment of the semiconductor chip with a first protective film of the present invention in which the shape of the bumps is not approximately spherical.
The semiconductor chip 3 with a first protective film shown here is the same as the semiconductor chip 1 with a first protective film shown in FIG. 1 except that the semiconductor chip 3 with the first protective film is provided with bumps 92 instead of the bumps 91 (that is, the shapes of the bumps are different). is there.
More specifically, in the bumps 91 shown in FIG. 1, the bumps 92 are such that the tops 910 are not curved but flat. That is, the tops 920 of the bumps 92 are flat.
In FIG. 3, reference numeral 92 a indicates the surface of the area of the bump 92 other than the crown portion 920.
　バンプ９２の頭頂部９２０の面は、例えば、半導体チップ９のバンプ形成面９ａに対して、平行であってもよいし、平行でなくてもよい。そして、平行でない場合、頭頂部９２０の面の向きは、特に限定されない。 For example, the surface of the top portion 920 of the bump 92 may or may not be parallel to the bump formation surface 9 a of the semiconductor chip 9. And if not parallel, the orientation of the surface of the crown 920 is not particularly limited.
　バンプ９２の頭頂部９２０は、第１保護膜１３を貫通して、突出している。さらに、バンプ９２の頭頂部９２０には、第１保護膜残留物が存在しない。したがって、バンプ９２の頭頂部９２０について、ＥＤＸ分析を行ったとき、Ｓ（Ｃ）／Ｓ（Ｓｎ）値は０．３２以下と、低水準となる。 Top portions 920 of the bumps 92 protrude through the first protective film 13. Furthermore, the top portion 920 of the bump 92 is free of the first protective film residue. Therefore, when EDX analysis is performed on the top of the head portion 920 of the bump 92, the S (C) / S (Sn) value becomes as low as 0.32 or less.
　バンプ９２の幅と、隣り合うバンプ９２間の距離は、図１に示すバンプ９１の場合と同じである。 The width of the bumps 92 and the distance between the adjacent bumps 92 are the same as in the case of the bumps 91 shown in FIG.
　バンプ９２の高さは特に限定されないが、４０～３９０μｍであることが好ましく、７０～２５０μｍであることがより好ましく、１３０～１９０μｍであることが特に好ましい。バンプ９２の高さが前記下限値以上であることで、バンプ９２の機能をより向上させることができる。また、バンプ９２の高さが前記上限値以下であることで、バンプ９２の頭頂部９２０における、第１保護膜残留物の残存を抑制する効果がより高くなる。 The height of the bumps 92 is not particularly limited, but is preferably 40 to 390 μm, more preferably 70 to 250 μm, and particularly preferably 130 to 190 μm. When the height of the bump 92 is equal to or more than the lower limit value, the function of the bump 92 can be further improved. Further, when the height of the bumps 92 is equal to or less than the upper limit value, the effect of suppressing the remaining of the first protective film residue in the top portion 920 of the bumps 92 becomes higher.
　ここでは、第１保護膜付き半導体チップとして、バンプの頭頂部に、第１保護膜残留物が存在しないものについて示しているが、本発明の第１保護膜付き半導体チップは、バンプの頭頂部に、第１保護膜残留物が少量存在したものであってもよい。このときの第１保護膜残留物の量は、上述のように少なければよい。 Here, although the semiconductor chip with a first protective film is shown for the one in which the first protective film residue is not present on the top of the bump, the semiconductor chip with a first protective film of the present invention is the top of the bump. In addition, a small amount of the first protective film residue may be present. The amount of the first protective film residue at this time may be small as described above.
　図４は、本発明の第１保護膜付き半導体チップのうち、バンプの頭頂部に第１保護膜残留物が少量存在している場合の一実施形態を模式的に示す拡大断面図である。
　ここに示す第１保護膜付き半導体チップ４は、バンプ９２の頭頂部９２０に、第１保護膜残留物１３１が少量存在している点以外は、図３に示す第１保護膜付き半導体チップ３と同じである。 FIG. 4 is an enlarged sectional view schematically showing an embodiment in the case where a small amount of the first protective film residue is present at the top of the bump in the semiconductor chip with the first protective film of the present invention.
The semiconductor chip 4 with a first protective film shown here is the semiconductor chip 3 with a first protective film shown in FIG. 3 except that a small amount of the first protective film residue 131 is present on the top portion 920 of the bump 92. Is the same as
　第１保護膜付き半導体チップ４は、第１保護膜残留物１３１が残存しているものの、バンプ９２の頭頂部９２０は、第１保護膜１３を貫通して、突出している。
　第１保護膜付き半導体チップ４は、バンプ９２の頭頂部９２０において、第１保護膜残留物１３１の量が少なく、第１保護膜残留物１３１の残存が抑制されている。したがって、バンプ９２の頭頂部９２０について、ＥＤＸ分析を行ったとき、Ｓ（Ｃ）／Ｓ（Ｓｎ）値は０．３２以下と、低水準となる。 Although the first protective film residue 131 remains in the first protective film-attached semiconductor chip 4, the top portion 920 of the bump 92 penetrates the first protective film 13 and protrudes.
In the first protective film-provided semiconductor chip 4, the amount of the first protective film residue 131 is small at the top portion 920 of the bump 92, and the remaining of the first protective film residue 131 is suppressed. Therefore, when EDX analysis is performed on the top of the head portion 920 of the bump 92, the S (C) / S (Sn) value becomes as low as 0.32 or less.
　第１保護膜付き半導体チップ４においては、第１保護膜残留物１３１が、バンプ９２の頭頂部９２０のうち、そのほぼ中央から、周囲の狭い領域に広がって存在している場合を示している。ただし、第１保護膜残留物１３１が存在する場合のその存在領域は、これに限定されず、例えば、バンプ９２のほぼ中央から、周囲の領域に広がって存在していなくてもよい。 In the first protective film-provided semiconductor chip 4, the case where the first protective film residue 131 is present in a narrow area around the center of the top portion 920 of the bump 92 is shown. . However, the present region in the case where the first protective film residue 131 is present is not limited to this, and for example, it may not be present from the approximate center of the bump 92 to the surrounding region.
　本発明の第１保護膜付き半導体チップは、図１～図４に示すものに限定されず、例えば、本発明の効果を損なわない範囲内において、図１～図４に示すものにおいて、一部の構成が変更、削除又は追加されたものであってもよい。
　例えば、図１～図４に示す第１保護膜付き半導体チップは、半導体チップ９の裏面９ｂに何も備えておらず、前記裏面９ｂは露出面となっているが、本発明の第１保護膜付き半導体チップは、半導体ウエハの裏面に保護膜（本明細書においては、「第２保護膜」と称することがある）等の何らかの層（膜）を備えていてもよい。 The semiconductor chip with a first protective film of the present invention is not limited to those shown in FIGS. 1 to 4 and, for example, some of the semiconductor chips shown in FIGS. 1 to 4 can be used as long as the effects of the present invention are not impaired. The configuration of may be changed, deleted or added.
For example, the semiconductor chip with a first protective film shown in FIGS. 1 to 4 has nothing on the back surface 9 b of the semiconductor chip 9 and the back surface 9 b is an exposed surface. The semiconductor chip with a film may be provided with any layer (film) such as a protective film (sometimes referred to as a “second protective film” in the present specification) on the back surface of the semiconductor wafer.
　第２保護膜は、上述の半導体チップを作製するために、半導体ウエハをダイシングしたときや、ダイシングによって得られた半導体チップをパッケージングして半導体装置を製造するまでの間に、半導体チップにおいてクラックが発生するのを防止する。
　第２保護膜は、通常、樹脂膜である。 The second protective film is a crack in the semiconductor chip when the semiconductor wafer is diced to produce the above-described semiconductor chip, or while the semiconductor chip obtained by the dicing is packaged to manufacture a semiconductor device. To prevent the occurrence of
The second protective film is usually a resin film.
　次に、第１保護膜付き半導体チップを構成する半導体チップ及び第１保護膜について、説明する。 Next, the semiconductor chip and the first protective film constituting the semiconductor chip with the first protective film will be described.
＜＜半導体チップ＞＞
　前記半導体チップは、バンプ形成面（回路を備える面、又は回路面とも称する）にバンプを有し、フリップチップ実装に用いることができるものであれば、特に限定されない。 << semiconductor chip >>
The semiconductor chip is not particularly limited as long as it has bumps on a bump formation surface (a surface provided with a circuit or also referred to as a circuit surface) and can be used for flip chip mounting.
　半導体チップのうち、バンプがその構成材料として含有する金属としては、スズ（Ｓｎ）が挙げられ、さらに、それ以外の金属としては、例えば、金（Ａｕ）、銀（Ａｇ）、銅（Ｃｕ）等が挙げられる。
　バンプの構成材料は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 Among the semiconductor chips, examples of the metal that the bump contains as its constituent material include tin (Sn), and as the other metals, for example, gold (Au), silver (Ag), copper (Cu) Etc.
The constituent material of the bumps may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
　バンプの形状、大きさ、配置状態は、先に説明したとおりである。 The shape, size, and arrangement of the bumps are as described above.
　半導体チップのうち、バンプを除いた部位の構成材料及び大きさは、公知のものと同じであってよい。
　例えば、半導体チップのバンプを除いた部位の厚さは、５０～７８０μｍであることが好ましく、１５０～４００μｍであることがより好ましい。 The constituent materials and sizes of the portions of the semiconductor chip excluding the bumps may be the same as known ones.
For example, the thickness of the portion of the semiconductor chip excluding the bumps is preferably 50 to 780 μm, and more preferably 150 to 400 μm.
＜＜第１保護膜＞＞
　第１保護膜付き半導体チップにおいて、第１保護膜は、半導体チップのバンプ形成面に密着するとともに、バンプの表面、特に半導体チップのバンプ形成面の近傍部位の表面を覆って、バンプを埋め込んでいる。第１保護膜は、このように、半導体チップのうち、バンプ形成面と、バンプのバンプ形成面の近傍部位の表面と、を被覆して、これらの領域を保護している。なお、バンプのバンプ形成面の近傍部位の表面と、第１保護膜と、の間には、一部、空隙部が存在することもある。 << First protective film >>
In the semiconductor chip with the first protective film, the first protective film adheres to the bump forming surface of the semiconductor chip and covers the surface of the bump, particularly the surface near the bump forming surface of the semiconductor chip to embed the bump. There is. As described above, the first protective film covers the bump formation surface and the surface of the vicinity of the bump formation surface of the bump in the semiconductor chip to protect these regions. There may be a void part between the surface of the vicinity of the bump formation surface of the bump and the first protective film.
　第１保護膜は、通常、樹脂成分を含有する樹脂膜であり、硬化によって第１保護膜を形成するための硬化性樹脂フィルムを用いて形成できる。そして、硬化性樹脂フィルムは、その構成材料を含有する硬化性樹脂フィルム形成用組成物を用いて形成できる。例えば、硬化性樹脂フィルムの形成対象面に対して、硬化性樹脂フィルム形成用組成物を塗工し、必要に応じて乾燥させることにより、目的とする箇所に硬化性樹脂フィルムを形成できる。硬化性樹脂フィルム形成用組成物中の、常温で気化しない成分同士の含有量の比率は、通常、硬化性樹脂フィルムの前記成分同士の含有量の比率と同じとなる。なお、本明細書において、「常温」とは、特に冷やしたり、熱したりしない温度、すなわち平常の温度を意味し、例えば、１５～２５℃の温度等が挙げられる。
　後述する熱硬化性樹脂フィルム形成用組成物及びエネルギー線硬化性樹脂フィルム形成用組成物中の樹脂に相当する成分は、すべて前記樹脂成分に包含される。
　このように、第１保護膜は、硬化性樹脂フィルム形成用組成物を用いて硬化性樹脂フィルムを形成した後、硬化性樹脂フィルムを硬化させることによって形成できる。 The first protective film is usually a resin film containing a resin component, and can be formed using a curable resin film for forming the first protective film by curing. And a curable resin film can be formed using the composition for curable resin film formation containing the constituent material. For example, the curable resin film-forming composition can be applied to the formation target surface of the curable resin film, and dried as needed, to form a curable resin film at a target location. The ratio of the contents of the components which do not vaporize at normal temperature in the composition for forming a curable resin film is usually the same as the ratio of the contents of the components of the curable resin film. In the present specification, “normal temperature” means a temperature which is not particularly cooled or heated, ie, a normal temperature, and includes, for example, a temperature of 15 to 25 ° C. and the like.
The components corresponding to the resin in the composition for forming a thermosetting resin film and the composition for forming an energy ray-curable resin film described later are all included in the resin component.
Thus, the first protective film can be formed by curing the curable resin film after forming the curable resin film using the curable resin film-forming composition.
　硬化性樹脂フィルム形成用組成物の塗工は、公知の方法で行えばよい。前記塗工方法としては、例えば、エアーナイフコーター、ブレードコーター、バーコーター、グラビアコーター、ロールコーター、ロールナイフコーター、カーテンコーター、ダイコーター、ナイフコーター、スクリーンコーター、マイヤーバーコーター、キスコーター等の各種コーターを用いる方法が挙げられる。 The coating of the curable resin film-forming composition may be performed by a known method. Examples of the coating method include various coaters such as an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, kiss coater, etc. The method of using
　硬化性樹脂フィルム形成用組成物の乾燥条件は、特に限定されず、前記組成物中の硬化性成分が目的外の硬化を起こさないように、適宜調節することが好ましい。
　例えば、硬化性樹脂フィルム形成用組成物は、後述する溶媒を含有している場合には、加熱乾燥させることが好ましい。溶媒を含有する硬化性樹脂フィルム形成用組成物は、例えば、７０～１３０℃で１０秒～５分の条件で乾燥させることが好ましい。 The drying conditions of the composition for forming a curable resin film are not particularly limited, and it is preferable to appropriately adjust so that the curable component in the composition does not cause curing other than the purpose.
For example, when the composition for curable resin film formation contains the solvent mentioned later, it is preferable to make it heat-dry. The composition for forming a curable resin film containing a solvent is preferably dried, for example, at 70 to 130 ° C. for 10 seconds to 5 minutes.
　第１保護膜は１層（単層）のみでもよいし、２層以上の複数層でもよく、複数層である場合、これら複数層は、互いに同一でも異なっていてもよく、これら複数層の組み合わせは特に限定されない。
　なお、本明細書においては、第１保護膜の場合に限らず、「複数層が互いに同一でも異なっていてもよい」とは、「すべての層が同一であってもよいし、すべての層が異なっていてもよく、一部の層のみが同一であってもよい」ことを意味し、さらに「複数層が互いに異なる」とは、「各層の構成材料及び厚さの少なくとも一方が互いに異なる」ことを意味する。 The first protective film may be only one layer (single layer) or may be a plurality of layers of two or more layers, and in the case of a plurality of layers, the plurality of layers may be the same or different from each other, and a combination of these layers Is not particularly limited.
In the present specification, not only in the case of the first protective film, but “a plurality of layers may be the same as or different from each other” means “all layers may be the same or all layers. May mean that only some of the layers may be the same, and further, “a plurality of layers are different from each other” means “at least one of the constituent material and thickness of each layer is different from each other” "Means.
　第１保護膜の厚さは、１～１００μｍであることが好ましく、５～７５μｍであることがより好ましく、５～５０μｍであることが特に好ましい。第１保護膜の厚さが前記下限値以上であることで、第１保護膜の保護能がより高くなる。第１保護膜の厚さが前記上限値以下であることで、バンプの頭頂部において、第１保護膜残留物の残存を抑制する効果がより高くなる。
　ここで、「第１保護膜の厚さ」とは、第１保護膜全体の厚さを意味し、例えば、複数層からなる第１保護膜の厚さとは、第１保護膜を構成するすべての層の合計の厚さを意味する。 The thickness of the first protective film is preferably 1 to 100 μm, more preferably 5 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the first protective film is not less than the lower limit value, the protective ability of the first protective film becomes higher. When the thickness of the first protective film is equal to or less than the upper limit value, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
Here, "the thickness of the first protective film" means the thickness of the entire first protective film, and for example, the thickness of the first protective film composed of a plurality of layers means all of the components of the first protective film. Means the total thickness of the layers.
　第１保護膜は、熱硬化性樹脂フィルムの硬化物及びエネルギー線硬化性樹脂フィルムの硬化物のいずれであってもよい。すなわち、第１保護膜は、熱硬化性樹脂フィルム形成用組成物及びエネルギー線硬化性樹脂フィルム形成用組成物のいずれを用いて形成されたものであってもよい。 The first protective film may be either a cured product of a thermosetting resin film or a cured product of an energy ray curable resin film. That is, the first protective film may be formed using any of the thermosetting resin film forming composition and the energy ray curable resin film forming composition.
　なお、本明細書において、「エネルギー線」とは、電磁波又は荷電粒子線の中でエネルギー量子を有するものを意味し、その例として、紫外線、放射線、電子線等が挙げられる。
　紫外線は、例えば、紫外線源として高圧水銀ランプ、ヒュージョンランプ、キセノンランプ、ブラックライト又はＬＥＤランプ等を用いることで照射できる。電子線は、電子線加速器等によって発生させたものを照射できる。
　本発明において、「エネルギー線硬化性」とは、エネルギー線を照射することにより硬化する性質を意味し、「非エネルギー線硬化性」とは、エネルギー線を照射しても硬化しない性質を意味する。 In the present specification, the term "energy beam" means one having an energy quantum among electromagnetic waves or charged particle beams, and examples thereof include ultraviolet rays, radiation, electron beams and the like.
The ultraviolet light can be irradiated, for example, by using a high pressure mercury lamp, a fusion lamp, a xenon lamp, a black light or an LED lamp as an ultraviolet light source. The electron beam can irradiate what was generated by the electron beam accelerator or the like.
In the present invention, "energy ray curing property" means the property of curing by irradiation with energy rays, and "non energy ray curing property" means the property of not curing even by irradiation of energy rays. .
◎熱硬化性樹脂フィルム形成用組成物
○樹脂層形成用組成物（ＩＩＩ）
　熱硬化性樹脂フィルム形成用組成物としては、例えば、重合体成分（Ａ）及び熱硬化性成分（Ｂ）を含有する熱硬化性樹脂フィルム形成用組成物（ＩＩＩ）（本明細書においては、単に「樹脂層形成用組成物（ＩＩＩ）」と略記することがある）等が挙げられる。 組成 Composition for forming thermosetting resin film ○ Composition for forming resin layer (III)
As the composition for forming a thermosetting resin film, for example, a composition for forming a thermosetting resin film (III) containing a polymer component (A) and a thermosetting component (B) (in the present specification, There may be mentioned simply as "the composition for forming a resin layer (III)" and the like.
［重合体成分（Ａ）］
　重合体成分（Ａ）は、熱硬化性樹脂フィルムに造膜性や可撓性等を付与するための重合体化合物であり、重合性化合物が重合反応して形成されたとみなせる成分である。なお、本明細書において重合反応には、重縮合反応も含まれる。
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムが含有する重合体成分（Ａ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 [Polymer component (A)]
The polymer component (A) is a polymer compound for imparting film forming property, flexibility and the like to a thermosetting resin film, and is a component which can be regarded as formed by polymerization reaction of a polymerizable compound. In the present specification, the polymerization reaction also includes a polycondensation reaction.
The polymer component (A) contained in the resin layer-forming composition (III) and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination thereof and The ratio can be selected arbitrarily.
　重合体成分（Ａ）としては、例えば、ポリビニルアセタール、アクリル系樹脂（（メタ）アクリロイル基を有する樹脂）等が挙げられる。 As a polymer component (A), polyvinyl acetal, acrylic resin (resin which has a (meth) acryloyl group) etc. are mentioned, for example.
　なお、本明細書において、「（メタ）アクリロイル基」とは、「アクリロイル基」及び「メタクリロイル基」の両方を包含する概念である。（メタ）アクリロイル基と類似の用語につても同様であり、例えば、「（メタ）アクリル酸」とは、「アクリル酸」及び「メタクリル酸」の両方を包含する概念であり、「（メタ）アクリレート」とは、「アクリレート」及び「メタクリレート」の両方を包含する概念である。 In the present specification, "(meth) acryloyl group" is a concept including both "acryloyl group" and "methacryloyl group". The same applies to terms similar to the (meth) acryloyl group, for example, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”, “(meth) acrylic acid”. The term "acrylate" is a concept encompassing both "acrylate" and "methacrylate".
　重合体成分（Ａ）における前記ポリビニルアセタールとしては、公知のものが挙げられる。
　なかでも、好ましいポリビニルアセタールとしては、例えば、ポリビニルホルマール、ポリビニルブチラール等が挙げられ、ポリビニルブチラールがより好ましい。
　ポリビニルブチラールとしては、下記式（ｉ）－１、（ｉ）－２及び（ｉ）－３で表される構成単位を有するものが挙げられる。 As said polyvinyl acetal in a polymer component (A), a well-known thing is mentioned.
Among them, preferable polyvinyl acetals include, for example, polyvinyl formal, polyvinyl butyral and the like, and polyvinyl butyral is more preferable.
As polyvinyl butyral, those having structural units represented by the following formulas (i) -1, (i) -2 and (i) -3 can be mentioned.
Figure JPOXMLDOC01-appb-C000001
 　（式中、ｌ、ｍ及びｎは、それぞれ独立に１以上の整数である。）
Figure JPOXMLDOC01-appb-C000001
 (Wherein, l, m and n are each independently an integer of 1 or more)
　ポリビニルアセタールの重量平均分子量（Ｍｗ）は、１０００００以下であることが好ましく、７００００以下であることがより好ましく、４００００以下であることが特に好ましい。ポリビニルアセタールの重量平均分子量がこのような範囲であることで、バンプの頭頂部において、第１保護膜残留物の残存を抑制する効果がより高くなる。 The weight average molecular weight (Mw) of the polyvinyl acetal is preferably 100,000 or less, more preferably 70,000 or less, and particularly preferably 40,000 or less. When the weight average molecular weight of the polyvinyl acetal is in such a range, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
　ポリビニルアセタールの重量平均分子量の下限値は、特に限定されない。ただし、第１保護膜の強度及び耐熱性がより向上する点では、ポリビニルアセタールの重量平均分子量は、５０００以上であることが好ましく、８０００以上であることがより好ましい。 The lower limit value of the weight average molecular weight of the polyvinyl acetal is not particularly limited. However, in terms of further improving the strength and heat resistance of the first protective film, the weight average molecular weight of the polyvinyl acetal is preferably 5000 or more, and more preferably 8000 or more.
　ポリビニルアセタールの重量平均分子量は、上述のいずれかの下限値及び上限値を任意に組み合わせて設定される範囲内となるように、適宜調節できる。
　例えば、一実施形態において、ポリビニルアセタールの重量平均分子量は、好ましくは５０００～１０００００、より好ましくは５０００～７００００、特に好ましくは５０００～４００００である。また、一実施形態において、ポリビニルアセタールの重量平均分子量は、好ましくは８０００～１０００００、より好ましくは８０００～７００００、特に好ましくは８０００～４００００である。ただし、これらは、ポリビニルアセタールの好ましい重量平均分子量の一例である。 The weight average molecular weight of the polyvinyl acetal can be appropriately adjusted so as to fall within the range set by arbitrarily combining any of the lower limit value and the upper limit value described above.
For example, in one embodiment, the weight average molecular weight of the polyvinyl acetal is preferably 5,000 to 100,000, more preferably 5,000 to 70000, and particularly preferably 5,000 to 40,000. In one embodiment, the weight average molecular weight of the polyvinyl acetal is preferably 8,000 to 100,000, more preferably 8,000 to 70,000, and particularly preferably 8,000 to 40,000. However, these are examples of the preferable weight average molecular weight of polyvinyl acetal.
　ポリビニルアセタールのガラス転移温度（Ｔｇ）は、４０～８０℃であることが好ましく、５０～７０℃であることがより好ましい。ポリビニルアセタールのＴｇがこのような範囲であることで、バンプの頭頂部において、第１保護膜残留物の残存を抑制する効果がより高くなる。 The glass transition temperature (Tg) of the polyvinyl acetal is preferably 40 to 80 ° C., and more preferably 50 to 70 ° C. When the Tg of the polyvinyl acetal is in such a range, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
　ポリビニルアセタールを構成する３種以上のモノマーの比率は任意に選択できる。 The ratio of three or more types of monomers constituting the polyvinyl acetal can be arbitrarily selected.
　重合体成分（Ａ）における前記アクリル系樹脂としては、公知のアクリル重合体が挙げられる。 Examples of the acrylic resin in the polymer component (A) include known acrylic polymers.
　アクリル系樹脂の重量平均分子量（Ｍｗ）は、３０００００以下であることが好ましく、１５００００以下であることがより好ましく、１０００００以下であることが特に好ましい。アクリル系樹脂の重量平均分子量がこのような範囲であることで、バンプの頭頂部において、第１保護膜残留物の残存を抑制する効果がより高くなる。 The weight average molecular weight (Mw) of the acrylic resin is preferably 300000 or less, more preferably 150,000 or less, and particularly preferably 100,000 or less. When the weight average molecular weight of the acrylic resin is in such a range, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
　アクリル系樹脂の重量平均分子量の下限値は、特に限定されない。ただし、第１保護膜の強度及び耐熱性がより向上する点では、アクリル系樹脂の重量平均分子量は、１００００以上であることが好ましく、３００００以上であることがより好ましい。 The lower limit value of the weight average molecular weight of the acrylic resin is not particularly limited. However, from the viewpoint of further improving the strength and heat resistance of the first protective film, the weight average molecular weight of the acrylic resin is preferably 10000 or more, and more preferably 30000 or more.
　アクリル系樹脂の重量平均分子量は、上述のいずれかの下限値及び上限値を任意に組み合わせて設定される範囲内となるように、適宜調節できる。
　例えば、一実施形態において、アクリル系樹脂の重量平均分子量は、好ましくは１００００～３０００００、より好ましくは１００００～１５００００、特に好ましくは１００００～１０００００である。また、一実施形態において、アクリル系樹脂の重量平均分子量は、好ましくは３００００～３０００００、より好ましくは３００００～１５００００、特に好ましくは３００００～１０００００である。ただし、これらは、アクリル系樹脂の好ましい重量平均分子量の一例である。 The weight average molecular weight of the acrylic resin can be appropriately adjusted so as to fall within a range set by arbitrarily combining any of the lower limit value and the upper limit value described above.
For example, in one embodiment, the weight average molecular weight of the acrylic resin is preferably 10,000 to 300,000, more preferably 10,000 to 150,000, and particularly preferably 10,000 to 100,000. In one embodiment, the weight average molecular weight of the acrylic resin is preferably 30,000 to 300,000, more preferably 30,000 to 150,000, and particularly preferably 30,000 to 100,000. However, these are examples of the preferable weight average molecular weight of acrylic resin.
　アクリル系樹脂のガラス転移温度（Ｔｇ）は、－５０～７０℃であることが好ましく、－３０～６０℃であることがより好ましい。アクリル系樹脂のＴｇがこのような範囲であることで、バンプの頭頂部において、第１保護膜残留物の残存を抑制する効果がより高くなる。 The glass transition temperature (Tg) of the acrylic resin is preferably −50 to 70 ° C., and more preferably −30 to 60 ° C. When the Tg of the acrylic resin is in such a range, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
　アクリル系樹脂を構成するモノマーは、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The monomer constituting the acrylic resin may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
　アクリル系樹脂としては、例えば、１種又は２種以上の（メタ）アクリル酸エステルの重合体；
　（メタ）アクリル酸、イタコン酸、酢酸ビニル、アクリロニトリル、スチレン及びＮ－メチロールアクリルアミド等から選択される２種以上のモノマーの共重合体；
　１種又は２種以上の（メタ）アクリル酸エステルと、（メタ）アクリル酸、イタコン酸、酢酸ビニル、アクリロニトリル、スチレン及びＮ－メチロールアクリルアミド等から選択される１種又は２種以上のモノマーと、の共重合体等が挙げられる。 As the acrylic resin, for example, a polymer of one or more kinds of (meth) acrylic acid esters;
(Meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and copolymers of two or more monomers selected from N-methylol acrylamide and the like;
1 type or 2 or more types of (meth) acrylic acid ester, 1 type or 2 or more types of monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylol acrylamide and the like, And the like.
　アクリル系樹脂を構成する前記（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓｅｃ－ブチル、（メタ）アクリル酸ｔｅｒｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸ｎ－ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル（（メタ）アクリル酸ラウリル）、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル（（メタ）アクリル酸ミリスチル）、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル（（メタ）アクリル酸パルミチル）、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル（（メタ）アクリル酸ステアリル）等の、アルキルエステルを構成するアルキル基が、炭素数が１～１８の鎖状構造である（メタ）アクリル酸アルキルエステル；
　（メタ）アクリル酸イソボルニル、（メタ）アクリル酸ジシクロペンタニル等の（メタ）アクリル酸シクロアルキルエステル；
　（メタ）アクリル酸ベンジル等の（メタ）アクリル酸アラルキルエステル；
　（メタ）アクリル酸ジシクロペンテニルエステル等の（メタ）アクリル酸シクロアルケニルエステル；
　（メタ）アクリル酸ジシクロペンテニルオキシエチルエステル等の（メタ）アクリル酸シクロアルケニルオキシアルキルエステル；
　（メタ）アクリル酸イミド；
　（メタ）アクリル酸グリシジル等のグリシジル基含有（メタ）アクリル酸エステル；
　（メタ）アクリル酸ヒドロキシメチル、（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３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシブチル等の水酸基含有（メタ）アクリル酸エステル；
　（メタ）アクリル酸Ｎ－メチルアミノエチル等の置換アミノ基含有（メタ）アクリル酸エステル等が挙げられる。ここで、「置換アミノ基」とは、アミノ基の１個又は２個の水素原子が水素原子以外の基で置換されてなる基を意味する。 Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic Heptyl acid, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , (Meth) acrylic acid undecyl, (meth) acrylic acid dodecyl ((meth) acrylic acid Uryl), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), (meth) (Meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester such as heptadecyl acrylate or octadecyl (meth) acrylate (stearyl (meth) acrylate) has a chain structure of 1 to 18 carbon atoms;
(Meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid isobornyl, (meth) acrylic acid dicyclopentanyl;
(Meth) acrylic acid aralkyl esters such as benzyl (meth) acrylate;
(Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester;
(Meth) acrylic acid cycloalkenyloxy alkyl esters such as (meth) acrylic acid dicyclopentenyl oxyethyl ester;
(Meth) acrylic imides;
Glycidyl group-containing (meth) acrylic acid esters such as glycidyl (meth) acrylate;
Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth ) Hydroxyl-containing (meth) acrylic acid esters such as 3-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate;
Examples thereof include substituted amino group-containing (meth) acrylic acid esters such as N-methylaminoethyl (meth) acrylic acid. Here, "substituted amino group" means a group obtained by substituting one or two hydrogen atoms of an amino group with a group other than a hydrogen atom.
　アクリル系樹脂は、ビニル基、（メタ）アクリロイル基、アミノ基、水酸基、カルボキシ基、イソシアネート基等の他の化合物と結合可能な官能基を有していてもよい。アクリル系樹脂の前記官能基は、後述する架橋剤（Ｆ）を介して他の化合物と結合してもよいし、架橋剤（Ｆ）を介さずに他の化合物と直接結合していてもよい。アクリル系樹脂が前記官能基により他の化合物と結合することで、第１保護膜を用いて得られたパッケージの信頼性が向上する傾向がある。 The acrylic resin may have a functional group capable of binding to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group and an isocyanate group. The functional group of the acrylic resin may be bonded to another compound through a crosslinking agent (F) described later, or may be directly bonded to another compound without the crosslinking agent (F) . There is a tendency for the reliability of the package obtained using the first protective film to be improved by the acrylic resin being bonded to another compound through the functional group.
　樹脂層形成用組成物（ＩＩＩ）において、溶媒以外の全ての成分の総含有量に対する重合体成分（Ａ）の含有量の割合（すなわち、熱硬化性樹脂フィルムの重合体成分（Ａ）の含有量）は、重合体成分（Ａ）の種類によらず、５～２５質量％であることが好ましく、５～１５質量％であることがより好ましい。 In the composition (III) for forming a resin layer, the ratio of the content of the polymer component (A) to the total content of all the components other than the solvent (that is, the content of the polymer component (A) of the thermosetting resin film) The amount of (5) is preferably 5 to 25% by mass, and more preferably 5 to 15% by mass, regardless of the type of the polymer component (A).
［熱硬化性成分（Ｂ）］
　熱硬化性成分（Ｂ）は、熱を反応のトリガーとして、熱硬化性樹脂フィルムを硬化させて、硬質の第１保護膜を形成するための成分である。
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムが含有する熱硬化性成分（Ｂ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 [Thermosetting component (B)]
The thermosetting component (B) is a component for curing the thermosetting resin film using heat as a trigger for the reaction to form a hard first protective film.
The thermosetting component (B) contained in the resin layer-forming composition (III) and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination thereof And the ratio can be selected arbitrarily.
　熱硬化性成分（Ｂ）は、エポキシ系熱硬化性樹脂であることが好ましい。 The thermosetting component (B) is preferably an epoxy-based thermosetting resin.
（エポキシ系熱硬化性樹脂）
　エポキシ系熱硬化性樹脂は、エポキシ樹脂（Ｂ１）及び熱硬化剤（Ｂ２）からなる。
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムが含有するエポキシ系熱硬化性樹脂は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 (Epoxy-based thermosetting resin)
The epoxy-based thermosetting resin comprises an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy-based thermosetting resin contained in the composition (III) for forming a resin layer and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination thereof and The ratio can be selected arbitrarily.
・エポキシ樹脂（Ｂ１）
　エポキシ樹脂（Ｂ１）としては、公知のものが挙げられ、例えば、多官能系エポキシ樹脂、ビフェニル化合物、ビスフェノールＡジグリシジルエーテル及びその水添物、オルソクレゾールノボラックエポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェニレン骨格型エポキシ樹脂等、２官能以上のエポキシ化合物が挙げられる。 ・ Epoxy resin (B1)
As an epoxy resin (B1), a well-known thing is mentioned, For example, a polyfunctional epoxy resin, a biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated substance, an ortho cresol novolak epoxy resin, a dicyclopentadiene type epoxy resin, The bifunctional or more epoxy compound such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. may be mentioned.
　エポキシ樹脂（Ｂ１）は、不飽和炭化水素基を有するエポキシ樹脂であってもよい。不飽和炭化水素基を有するエポキシ樹脂は、不飽和炭化水素基を有しないエポキシ樹脂よりもアクリル系樹脂との相溶性が高い。そのため、不飽和炭化水素基を有するエポキシ樹脂と、アクリル系樹脂と、を含有する第１保護膜を用いて得られたパッケージの信頼性が向上する。 The epoxy resin (B1) may be an epoxy resin having an unsaturated hydrocarbon group. An epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained using the first protective film containing an epoxy resin having an unsaturated hydrocarbon group and an acrylic resin is improved.
　不飽和炭化水素基を有するエポキシ樹脂としては、例えば、多官能系エポキシ樹脂のエポキシ基の一部が不飽和炭化水素基を有する基に変換されてなる化合物が挙げられる。このような化合物は、例えば、エポキシ基へ（メタ）アクリル酸又はその誘導体を付加反応させることにより得られる。
　また、不飽和炭化水素基を有するエポキシ樹脂としては、例えば、エポキシ樹脂を構成する芳香環等に、不飽和炭化水素基を有する基が直接結合した化合物等が挙げられる。
　不飽和炭化水素基は、重合性を有する不飽和基であり、その具体的な例としては、エテニル基（ビニル基）、２－プロペニル基（アリル基）、（メタ）アクリロイル基、（メタ）アクリルアミド基等が挙げられ、アクリロイル基が好ましい。 As an epoxy resin which has an unsaturated hydrocarbon group, the compound formed by converting a part of epoxy group of polyfunctional epoxy resin into the group which has an unsaturated hydrocarbon group is mentioned, for example. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group.
Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple | bonded with the aromatic ring which comprises an epoxy resin, etc. are mentioned, for example.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth) acryloyl group, (meth) An acrylamide group etc. are mentioned and an acryloyl group is preferable.
　エポキシ樹脂（Ｂ１）の重量平均分子量は、３００００以下であることが好ましく、２００００以下であることがより好ましく、１００００以下であることが特に好ましい。エポキシ樹脂（Ｂ１）の重量平均分子量が前記上限値以下であることで、バンプの頭頂部において、第１保護膜残留物の残存を抑制する効果がより高くなる。 The weight average molecular weight of the epoxy resin (B1) is preferably 30,000 or less, more preferably 20,000 or less, and particularly preferably 10,000 or less. When the weight average molecular weight of the epoxy resin (B1) is less than or equal to the upper limit value, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
　エポキシ樹脂（Ｂ１）の重量平均分子量の下限値は、特に限定されない。ただし、熱硬化性樹脂フィルムの硬化性、並びに第１保護膜の強度及び耐熱性がより向上する点では、エポキシ樹脂（Ｂ１）の重量平均分子量は、３００以上であることが好ましく、５００以上であることがより好ましい。 The lower limit value of the weight average molecular weight of the epoxy resin (B1) is not particularly limited. However, the weight average molecular weight of the epoxy resin (B1) is preferably 300 or more, and preferably 500 or more, in that the curability of the thermosetting resin film and the strength and heat resistance of the first protective film are further improved. It is more preferable that
　エポキシ樹脂（Ｂ１）の重量平均分子量は、上述のいずれかの下限値及び上限値を任意に組み合わせて設定される範囲内となるように、適宜調節できる。
　例えば、一実施形態において、エポキシ樹脂（Ｂ１）の重量平均分子量は、好ましくは３００～３００００、より好ましくは３００～２００００、特に好ましくは３００～１００００である。また、一実施形態において、エポキシ樹脂（Ｂ１）の重量平均分子量は、好ましくは５００～３００００、より好ましくは５００～２００００、特に好ましくは５００～１００００である。ただし、これらは、エポキシ樹脂（Ｂ１）の好ましい重量平均分子量の一例である。 The weight average molecular weight of the epoxy resin (B1) can be appropriately adjusted so as to fall within the range set by arbitrarily combining any of the lower limit value and the upper limit value described above.
For example, in one embodiment, the weight average molecular weight of the epoxy resin (B1) is preferably 300 to 30,000, more preferably 300 to 20,000, and particularly preferably 300 to 10,000. In one embodiment, the weight average molecular weight of the epoxy resin (B1) is preferably 500 to 30,000, more preferably 500 to 20,000, and particularly preferably 500 to 10,000. However, these are examples of the preferable weight average molecular weight of an epoxy resin (B1).
　エポキシ樹脂（Ｂ１）のエポキシ当量は、１００～１０００ｇ／ｅｑであることが好ましく、３００～８００ｇ／ｅｑであることがより好ましい。 The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000 g / eq, and more preferably 300 to 800 g / eq.
　エポキシ樹脂（Ｂ１）は、常温で液状であるもの（本明細書においては、単に「液状のエポキシ樹脂（Ｂ１）」と称することがある）が好ましい。このようなエポキシ樹脂（Ｂ１）を用いることで、バンプの頭頂部において、第１保護膜残留物の残存を抑制する効果がより高くなる。 The epoxy resin (B1) is preferably one that is liquid at normal temperature (sometimes referred to herein simply as "liquid epoxy resin (B1)"). By using such an epoxy resin (B1), the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
　エポキシ樹脂（Ｂ１）は、１種を単独で用いてもよいし、２種以上を併用してもよく、２種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。 An epoxy resin (B1) may be used individually by 1 type, and 2 or more types may be used together, and when using 2 or more types together, the combination and ratio of those can be selected arbitrarily.
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムが含有する、エポキシ樹脂（Ｂ１）のうち、液状のエポキシ樹脂（Ｂ１）の割合は、４０質量％以上であることが好ましく、５０質量％以上であることがより好ましく、５５質量％以上であることが特に好ましく、例えば、６０質量％以上、７０質量％以上、８０質量％以上及び９０質量％以上のいずれかであってもよい。前記割合が前記下限値以上であることで、バンプの頭頂部において、第１保護膜残留物の残存を抑制する効果がより高くなる。
　前記割合の上限値は特に限定されず、前記割合は１００質量％以下であればよい。 The proportion of the liquid epoxy resin (B1) in the epoxy resin (B1) contained in the resin layer-forming composition (III) and the thermosetting resin film is preferably 40% by mass or more, and 50% by mass % Or more, more preferably 55% by mass or more, for example, 60% by mass or more, 70% by mass or more, 80% by mass or more, and 90% by mass or more. When the ratio is equal to or more than the lower limit value, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
The upper limit of the ratio is not particularly limited, and the ratio may be 100% by mass or less.
・熱硬化剤（Ｂ２）
　熱硬化剤（Ｂ２）は、エポキシ樹脂（Ｂ１）に対する硬化剤として機能する。
　熱硬化剤（Ｂ２）としては、例えば、１分子中にエポキシ基と反応し得る官能基を２個以上有する化合物が挙げられる。前記官能基としては、例えば、フェノール性水酸基、アルコール性水酸基、アミノ基、カルボキシ基、酸基が無水物化された基等が挙げられ、フェノール性水酸基、アミノ基、又は酸基が無水物化された基であることが好ましく、フェノール性水酸基又はアミノ基であることがより好ましい。 ・ Heat curing agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
As a thermosetting agent (B2), the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, and a group in which an acid group is anhydrated, and the phenolic hydroxyl group, an amino group, or an acid group is anhydrated. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.
　熱硬化剤（Ｂ２）のうち、フェノール性水酸基を有するフェノール系硬化剤としては、例えば、多官能フェノール樹脂、ビフェノール、ノボラック型フェノール樹脂、ジシクロペンタジエン系フェノール樹脂、アラルキルフェノール樹脂等が挙げられる。
　熱硬化剤（Ｂ２）のうち、アミノ基を有するアミン系硬化剤としては、例えば、ジシアンジアミド（以下、「ＤＩＣＹ」と略記することがある）等が挙げられる。 Among the thermosetting agents (B2), as a phenol-based curing agent having a phenolic hydroxyl group, for example, polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-based phenol resins, aralkylphenol resins and the like can be mentioned.
Examples of the amine-based curing agent having an amino group among the heat curing agents (B2) include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).
　熱硬化剤（Ｂ２）は、不飽和炭化水素基を有するものでもよい。
　不飽和炭化水素基を有する熱硬化剤（Ｂ２）としては、例えば、フェノール樹脂の水酸基の一部が、不飽和炭化水素基を有する基で置換されてなる化合物、フェノール樹脂の芳香環に、不飽和炭化水素基を有する基が直接結合してなる化合物等が挙げられる。
　熱硬化剤（Ｂ２）における前記不飽和炭化水素基は、上述の不飽和炭化水素基を有するエポキシ樹脂における不飽和炭化水素基と同様のものである。 The thermosetting agent (B2) may have an unsaturated hydrocarbon group.
As the thermosetting agent (B2) having an unsaturated hydrocarbon group, for example, a compound obtained by substituting a part of hydroxyl groups of a phenol resin with a group having an unsaturated hydrocarbon group, an aromatic ring of a phenol resin, The compound etc. which a group which has a saturated hydrocarbon group directly couple | bonds are mentioned.
The said unsaturated hydrocarbon group in a thermosetting agent (B2) is a thing similar to the unsaturated hydrocarbon group in the epoxy resin which has the above-mentioned unsaturated hydrocarbon group.
　熱硬化剤（Ｂ２）のうち、例えば、多官能フェノール樹脂、ノボラック型フェノール樹脂、ジシクロペンタジエン系フェノール樹脂、アラルキルフェノール樹脂等の樹脂成分の数平均分子量は、３００～３００００であることが好ましく、４００～１００００であることがより好ましく、５００～５０００であることが特に好ましい。
　熱硬化剤（Ｂ２）のうち、例えば、ビフェノール、ジシアンジアミド等の非樹脂成分の分子量は、特に限定されないが、例えば、６０～５００であることが好ましい。 Among the thermosetting agents (B2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, aralkyl phenol resin and the like is preferably 300 to 30000, It is more preferably 400 to 10,000, and particularly preferably 500 to 5,000.
Among the thermosetting agents (B2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.
　熱硬化剤（Ｂ２）は、１種を単独で用いてもよいし、２種以上を併用してもよく、２種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。 A thermosetting agent (B2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and a ratio can be selected arbitrarily.
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムにおいて、熱硬化剤（Ｂ２）の含有量は、エポキシ樹脂（Ｂ１）の含有量１００質量部に対して、０．１～５００質量部であることが好ましく、１～２００質量部であることがより好ましく、例えば、１～１５０質量部、１～１００質量部、１～７５質量部、１～５０質量部、及び１～３０質量部のいずれかであってもよい。熱硬化剤（Ｂ２）の前記含有量が前記下限値以上であることで、熱硬化性樹脂フィルムの硬化がより進行し易くなる。また、熱硬化剤（Ｂ２）の前記含有量が前記上限値以下であることで、熱硬化性樹脂フィルムの吸湿率が低減されて、第１保護膜を用いて得られたパッケージの信頼性がより向上する。 In the composition for forming a resin layer (III) and the thermosetting resin film, the content of the thermosetting agent (B2) is 0.1 to 500 parts by mass with respect to 100 parts by mass of the epoxy resin (B1). Is preferably 1 to 200 parts by mass, and more preferably 1 to 150 parts by mass, 1 to 100 parts by mass, 1 to 75 parts by mass, 1 to 50 parts by mass, and 1 to 30 parts by mass. It may be any of the above. When the content of the thermosetting agent (B2) is equal to or more than the lower limit value, curing of the thermosetting resin film becomes easier to progress. In addition, when the content of the thermosetting agent (B2) is not more than the upper limit value, the moisture absorption rate of the thermosetting resin film is reduced, and the reliability of the package obtained using the first protective film is It improves more.
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムにおいて、熱硬化性成分（Ｂ）の含有量（例えば、エポキシ樹脂（Ｂ１）及び熱硬化剤（Ｂ２）の総含有量）は、重合体成分（Ａ）の含有量１００質量部に対して、６００～１０００質量部であることが好ましい。熱硬化性成分（Ｂ）の前記含有量がこのような範囲であることで、バンプの頭頂部において、第１保護膜残留物の残存を抑制する効果がより高くなり、かつ硬質な第１保護膜を形成できる。
　さらに、このような効果がより顕著に得られる点から、熱硬化性成分（Ｂ）の含有量は、重合体成分（Ａ）の種類に応じて、適宜調節することが好ましい。 In the composition (III) for forming a resin layer and the thermosetting resin film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is heavy The amount is preferably 600 to 1000 parts by mass with respect to 100 parts by mass of the content of the united component (A). When the content of the thermosetting component (B) is in such a range, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump, and the hard first protection It can form a film.
Furthermore, it is preferable that the content of the thermosetting component (B) be appropriately adjusted in accordance with the type of the polymer component (A) from the viewpoint that such effects can be obtained more remarkably.
　例えば、重合体成分（Ａ）が前記ポリビニルアセタールである場合、樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムにおいて、熱硬化性成分（Ｂ）の含有量は、重合体成分（Ａ）の含有量１００質量部に対して、６００～１０００質量部であることが好ましく、６５０～１０００質量部であることがより好ましく、６５０～９５０質量部であることが特に好ましい。 For example, when the polymer component (A) is the polyvinyl acetal, the content of the thermosetting component (B) in the resin layer-forming composition (III) and the thermosetting resin film is the polymer component (A). The amount is preferably 600 to 1000 parts by mass, more preferably 650 to 1000 parts by mass, and particularly preferably 650 to 950 parts by mass with respect to 100 parts by mass of the content of
　例えば、重合体成分（Ａ）が前記アクリル系樹脂である場合、樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムにおいて、熱硬化性成分（Ｂ）の含有量は、重合体成分（Ａ）の含有量１００質量部に対して、７００～１０００質量部であることが好ましく、７５０～１０００質量部であることがより好ましく、７５０～９００質量部であることが特に好ましい。 For example, when the polymer component (A) is the acrylic resin, the content of the thermosetting component (B) in the resin layer-forming composition (III) and the thermosetting resin film is the polymer component (B). The amount is preferably 700 to 1000 parts by mass, more preferably 750 to 1000 parts by mass, and particularly preferably 750 to 900 parts by mass with respect to 100 parts by mass of the content of A).
［硬化促進剤（Ｃ）］
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムは、硬化促進剤（Ｃ）を含有することが好ましい。硬化促進剤（Ｃ）は、樹脂層形成用組成物（ＩＩＩ）の硬化速度を調整するための成分である。
　好ましい硬化促進剤（Ｃ）としては、例えば、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノール等の第３級アミン；２－メチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール等のイミダゾール類（１個以上の水素原子が水素原子以外の基で置換されたイミダゾール）；トリブチルホスフィン、ジフェニルホスフィン、トリフェニルホスフィン等の有機ホスフィン類（１個以上の水素原子が有機基で置換されたホスフィン）；テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレート等のテトラフェニルボロン塩等が挙げられる。 [Hardening accelerator (C)]
It is preferable that the composition for resin layer formation (III) and the thermosetting resin film contain a hardening accelerator (C). A hardening accelerator (C) is a component for adjusting the hardening speed of composition (III) for resin layer formation.
Preferred curing accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (one or more hydrogen atoms are not hydrogen atoms Imidazoles substituted with the following groups: organic phosphines such as tributyl phosphine, diphenyl phosphine, triphenyl phosphine (phosphines in which one or more hydrogen atoms are substituted with an organic group); tetraphenyl phosphonium tetraphenyl borate Tetraphenyl boron salts such as triphenyl phosphine tetraphenyl borate and the like.
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムが含有する硬化促進剤（Ｃ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The curing accelerator (C) contained in the resin layer-forming composition (III) and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination thereof and The ratio can be selected arbitrarily.
　硬化促進剤（Ｃ）を用いる場合、樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムにおいて、硬化促進剤（Ｃ）の含有量は、熱硬化性成分（Ｂ）の含有量１００質量部に対して、０．０１～１０質量部であることが好ましく、０．１～５質量部であることがより好ましい。硬化促進剤（Ｃ）の前記含有量が前記下限値以上であることで、硬化促進剤（Ｃ）を用いたことによる効果がより顕著に得られる。また、硬化促進剤（Ｃ）の含有量が前記上限値以下であることで、例えば、高極性の硬化促進剤（Ｃ）が、高温・高湿度条件下で熱硬化性樹脂フィルム中において被着体との接着界面側に移動して偏析することを抑制する効果が高くなり、第１保護膜を用いて得られたパッケージの信頼性がより向上する。 When using a curing accelerator (C), in the composition (III) for forming a resin layer and the thermosetting resin film, the content of the curing accelerator (C) is the content 100 mass of the thermosetting component (B) The amount is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass. The effect by using a hardening accelerator (C) is acquired more notably by the said content of a hardening accelerator (C) being more than the said lower limit. In addition, when the content of the curing accelerator (C) is equal to or less than the upper limit value, for example, the high-polarity curing accelerator (C) adheres to the thermosetting resin film under high temperature and high humidity conditions. The effect of suppressing migration and segregation to the adhesion interface side with the body is enhanced, and the reliability of the package obtained using the first protective film is further improved.
［充填材（Ｄ）］
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムは、充填材（Ｄ）を含有することが好ましい。充填材（Ｄ）を含有する第１保護膜は、熱膨張係数の調整が容易となる。例えば、第１保護膜の熱膨張係数を半導体チップに対して最適化することで、第１保護膜を用いて得られたパッケージの信頼性がより向上する。また、充填材（Ｄ）を含有する第１保護膜は、吸湿率を低減したり、放熱性を向上させたりすることもできる。 [Filler (D)]
The composition for forming a resin layer (III) and the thermosetting resin film preferably contain a filler (D). The first protective film containing the filler (D) facilitates adjustment of the thermal expansion coefficient. For example, by optimizing the thermal expansion coefficient of the first protective film with respect to the semiconductor chip, the reliability of the package obtained using the first protective film is further improved. The first protective film containing the filler (D) can also reduce the moisture absorption rate or improve the heat dissipation.
　充填材（Ｄ）は、有機充填材及び無機充填材のいずれでもよいが、無機充填材であることが好ましい。
　好ましい無機充填材としては、例えば、シリカ、アルミナ、タルク、炭酸カルシウム、チタンホワイト、ベンガラ、炭化ケイ素、窒化ホウ素等の粉末；これら無機充填材を球形化したビーズ；これら無機充填材の表面改質品；これら無機充填材の単結晶繊維；ガラス繊維等が挙げられる。
　これらの中でも、無機充填材は、シリカ又はアルミナであることが好ましい。 The filler (D) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide, boron nitride, etc .; spherical beads of these inorganic fillers; surface modification of these inorganic fillers Articles: single crystal fibers of these inorganic fillers; glass fibers and the like.
Among these, the inorganic filler is preferably silica or alumina.
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムが含有する充填材（Ｄ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The filler (D) contained in the resin layer-forming composition (III) and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination and ratio thereof Is optional.
　充填材（Ｄ）の平均粒径は、６μｍ以下であることが好ましく、例えば、４μｍ以下、２μｍ以下、及び０．５μｍ以下のいずれかであってもよい。充填材（Ｄ）の平均粒径が前記上限値以下であることで、バンプの頭頂部において、第１保護膜残留物の残存を抑制する効果がより高くなる。
　なお、本明細書において「平均粒径」とは、特に断りのない限り、レーザー回折散乱法によって求められた粒度分布曲線における、積算値５０％での粒子径（Ｄ５０）の値を意味する。 The average particle diameter of the filler (D) is preferably 6 μm or less, and may be, for example, any of 4 μm or less, 2 μm or less, and 0.5 μm or less. When the average particle diameter of the filler (D) is less than or equal to the upper limit value, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
In the present specification, “average particle diameter” means the value of the particle diameter (D 50 ) at an integrated value of 50% in the particle size distribution curve determined by the laser diffraction scattering method, unless otherwise specified. .
　充填材（Ｄ）の平均粒径の下限値は、特に限定されない。例えば、充填材（Ｄ）の平均粒径は、充填材（Ｄ）の入手がより容易である点では、０．０１μｍ以上であることが好ましい。 The lower limit of the average particle diameter of the filler (D) is not particularly limited. For example, the average particle diameter of the filler (D) is preferably 0.01 μm or more in that it is easier to obtain the filler (D).
　充填材（Ｄ）の平均粒径は、上述の下限値と、いずれかの上限値と、を任意に組み合わせて設定される範囲内となるように、適宜調節できる。
　例えば、充填材（Ｄ）の平均粒径は、好ましくは０．０１～６μｍであり、例えば、０．０１～４μｍ、０．０１～２μｍ、及び０．０１～０．５μｍのいずれかであってもよい。ただし、これは、充填材（Ｄ）の好ましい平均粒径の一例である。 The average particle diameter of the filler (D) can be appropriately adjusted so as to fall within the range set by arbitrarily combining the above lower limit value and any upper limit value.
For example, the average particle diameter of the filler (D) is preferably 0.01 to 6 μm, and for example, any of 0.01 to 4 μm, 0.01 to 2 μm, and 0.01 to 0.5 μm. May be However, this is an example of the preferable average particle diameter of filler (D).
　一方、充填材（Ｄ）を用いる場合、樹脂層形成用組成物（ＩＩＩ）において、溶媒以外の全ての成分の総含有量に対する充填材（Ｄ）の含有量の割合（すなわち、熱硬化性樹脂フィルムにおける、熱硬化性樹脂フィルムの総質量に対する、充填材（Ｄ）の含有量の割合）は、３～３０質量％であることがより好ましく、４～２０質量％であることがさらに好ましく、５～１５質量％であることが特に好ましい。充填材（Ｄ）の含有量がこのような範囲であることで、バンプの頭頂部において、第１保護膜残留物の残存を抑制する効果がより高くなるとともに、上記の熱膨張係数の調整がより容易となる。 On the other hand, in the case of using the filler (D), in the composition (III) for forming a resin layer, the ratio of the content of the filler (D) to the total content of all the components other than the solvent (that is, the thermosetting resin The ratio of the content of the filler (D) to the total mass of the thermosetting resin film in the film is more preferably 3 to 30% by mass, and still more preferably 4 to 20% by mass. Particularly preferred is 5 to 15% by mass. When the content of the filler (D) is in such a range, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump, and the adjustment of the thermal expansion coefficient is It will be easier.
［カップリング剤（Ｅ）］
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムは、カップリング剤（Ｅ）を含有していてもよい。カップリング剤（Ｅ）として、無機化合物又は有機化合物と反応可能な官能基を有するものを用いることにより、熱硬化性樹脂フィルムの被着体に対する接着性及び密着性を向上させることができる。また、カップリング剤（Ｅ）を含有する第１保護膜は、耐熱性を損なうことなく、耐水性が向上する。 [Coupling agent (E)]
The composition for resin layer formation (III) and the thermosetting resin film may contain a coupling agent (E). By using a coupling agent (E) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesion and adhesiveness of the thermosetting resin film to the adherend can be improved. Moreover, water resistance improves the 1st protective film containing a coupling agent (E), without impairing heat resistance.
　カップリング剤（Ｅ）は、重合体成分（Ａ）、熱硬化性成分（Ｂ）等が有する官能基と反応可能な官能基を有する化合物であることが好ましく、シランカップリング剤であることがより好ましい。
　好ましい前記シランカップリング剤としては、例えば、３－グリシジルオキシプロピルトリメトキシシラン、３－グリシジルオキシプロピルメチルジエトキシシラン、３－グリシジルオキシプロピルトリエトキシシラン、３－グリシジルオキシメチルジエトキシシラン、２－（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、３－メタクリロイルオキシプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－（２－アミノエチルアミノ）プロピルトリメトキシシラン、３－（２－アミノエチルアミノ）プロピルメチルジエトキシシラン、３－（フェニルアミノ）プロピルトリメトキシシラン、３－アニリノプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、ビス（３－トリエトキシシリルプロピル）テトラスルファン、メチルトリメトキシシラン、メチルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリアセトキシシラン、イミダゾールシラン等が挙げられる。 The coupling agent (E) is preferably a compound having a functional group capable of reacting with a functional group possessed by the polymer component (A), the thermosetting component (B) or the like, and is preferably a silane coupling agent. More preferable.
Preferred examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino) Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyl Trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, etc. Be
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムが含有するカップリング剤（Ｅ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The composition for forming a resin layer (III) and the coupling agent (E) contained in the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination thereof and The ratio can be selected arbitrarily.
　カップリング剤（Ｅ）を用いる場合、樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムにおいて、カップリング剤（Ｅ）の含有量は、重合体成分（Ａ）及び熱硬化性成分（Ｂ）の総含有量１００質量部に対して、０．０３～２０質量部であることが好ましく、０．０５～１０質量部であることがより好ましく、０．１～５質量部であることが特に好ましい。カップリング剤（Ｅ）の前記含有量が前記下限値以上であることで、充填材（Ｄ）の樹脂への分散性の向上や、熱硬化性樹脂フィルムの被着体との接着性の向上など、カップリング剤（Ｅ）を用いたことによる効果がより顕著に得られる。また、カップリング剤（Ｅ）の前記含有量が前記上限値以下であることで、アウトガスの発生がより抑制される。 When the coupling agent (E) is used, the content of the coupling agent (E) in the resin layer-forming composition (III) and the thermosetting resin film is the polymer component (A) and the thermosetting component ( It is preferable that it is 0.03-20 mass parts with respect to 100 mass parts of total content of B), It is more preferable that it is 0.05-10 mass parts, It is 0.1-5 mass parts Is particularly preferred. When the content of the coupling agent (E) is at least the lower limit value, the dispersibility of the filler (D) in the resin is improved, and the adhesion of the thermosetting resin film to the adherend is improved. The effect of using the coupling agent (E) is more remarkably obtained. Moreover, generation | occurrence | production of an outgas is suppressed more because the said content of a coupling agent (E) is below the said upper limit.
［架橋剤（Ｆ）］
　重合体成分（Ａ）として、他の化合物と結合可能なビニル基、（メタ）アクリロイル基、アミノ基、水酸基、カルボキシ基、イソシアネート基等の官能基を有するものを用いる場合、樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムは、架橋剤（Ｆ）を含有していてもよい。架橋剤（Ｆ）は、重合体成分（Ａ）中の前記官能基を他の化合物と結合させて架橋するための成分であり、このように架橋することにより、熱硬化性樹脂フィルムの初期接着力及び凝集力を調節できる。 [Crosslinking agent (F)]
When using what has functional groups, such as a vinyl group which can couple | bond with another compound, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group, an isocyanate group, as a polymer component (A), composition for resin layer formation The article (III) and the thermosetting resin film may contain a crosslinking agent (F). A crosslinking agent (F) is a component for making the said functional group in a polymer component (A) couple | bond with another compound, and bridge | crosslinking it, The initial adhesion of a thermosetting resin film is carried out by bridge | crosslinking in this way Force and cohesion can be adjusted.
　架橋剤（Ｆ）としては、例えば、有機多価イソシアネート化合物、有機多価イミン化合物、金属キレート系架橋剤（金属キレート構造を有する架橋剤）、アジリジン系架橋剤（アジリジニル基を有する架橋剤）等が挙げられる。 As the crosslinking agent (F), for example, organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate type crosslinking agents (crosslinking agents having a metal chelate structure), aziridine type crosslinking agents (crosslinking agents having an aziridinyl group), etc. Can be mentioned.
　前記有機多価イソシアネート化合物としては、例えば、芳香族多価イソシアネート化合物、脂肪族多価イソシアネート化合物及び脂環族多価イソシアネート化合物（以下、これら化合物をまとめて「芳香族多価イソシアネート化合物等」と略記することがある）；前記芳香族多価イソシアネート化合物等の三量体、イソシアヌレート体及びアダクト体；前記芳香族多価イソシアネート化合物等とポリオール化合物とを反応させて得られる末端イソシアネートウレタンプレポリマー等が挙げられる。前記「アダクト体」は、前記芳香族多価イソシアネート化合物、脂肪族多価イソシアネート化合物又は脂環族多価イソシアネート化合物と、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、トリメチロールプロパン又はヒマシ油等の低分子活性水素含有化合物との反応物を意味する。前記アダクト体の例としては、後述するようなトリメチロールプロパンのキシリレンジイソシアネート付加物等が挙げられる。また、「末端イソシアネートウレタンプレポリマー」とは、先に説明したとおりである。 As the organic polyvalent isocyanate compound, for example, an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound etc.” Abbreviated in some cases); trimers such as the above-mentioned aromatic polyvalent isocyanate compounds, isocyanurates and adducts; terminal isocyanate urethane prepolymers obtained by reacting the above-mentioned aromatic polyvalent isocyanate compounds and the like with a polyol compound Etc. The “adduct” includes the above-mentioned aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound or alicyclic polyvalent isocyanate compound, and low contents such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil It means a reactant with a molecule active hydrogen-containing compound. Examples of the adduct include xylylene diisocyanate adduct of trimethylolpropane as described later, and the like. In addition, the "terminal isocyanate urethane prepolymer" is as described above.
　前記有機多価イソシアネート化合物として、より具体的には、例えば、２，４－トリレンジイソシアネート；２，６－トリレンジイソシアネート；１，３－キシリレンジイソシアネート；１，４－キシレンジイソシアネート；ジフェニルメタン－４，４’－ジイソシアネート；ジフェニルメタン－２，４’－ジイソシアネート；３－メチルジフェニルメタンジイソシアネート；ヘキサメチレンジイソシアネート；イソホロンジイソシアネート；ジシクロヘキシルメタン－４，４’－ジイソシアネート；ジシクロヘキシルメタン－２，４’－ジイソシアネート；トリメチロールプロパン等のポリオールのすべて又は一部の水酸基に、トリレンジイソシアネート、ヘキサメチレンジイソシアネート及びキシリレンジイソシアネートのいずれか１種又は２種以上が付加した化合物；リジンジイソシアネート等が挙げられる。 More specifically, as the organic polyvalent isocyanate compound, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 Diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate in the hydroxyl groups of all or part of a polyol such as propane Or two or more compounds are added; lysine diisocyanate.
　前記有機多価イミン化合物としては、例えば、Ｎ，Ｎ’－ジフェニルメタン－４，４’－ビス（１－アジリジンカルボキシアミド）、トリメチロールプロパン－トリ－β－アジリジニルプロピオネート、テトラメチロールメタン－トリ－β－アジリジニルプロピオネート、Ｎ，Ｎ’－トルエン－２，４－ビス（１－アジリジンカルボキシアミド）トリエチレンメラミン等が挙げられる。 Examples of the organic polyhydric imine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinyl propionate, and tetramethylolmethane. -Tri-β-aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridine carboxamide) triethylene melamine and the like.
　架橋剤（Ｆ）として有機多価イソシアネート化合物を用いる場合、重合体成分（Ａ）としては、水酸基含有重合体を用いることが好ましい。架橋剤（Ｆ）がイソシアネート基を有し、重合体成分（Ａ）が水酸基を有する場合、架橋剤（Ｆ）と重合体成分（Ａ）との反応によって、熱硬化性樹脂フィルムに架橋構造を簡便に導入できる。 When using an organic polyhydric isocyanate compound as a crosslinking agent (F), it is preferable to use a hydroxyl-containing polymer as a polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, a crosslink structure is formed on the thermosetting resin film by the reaction of the crosslinking agent (F) with the polymer component (A). It can be introduced easily.
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムが含有する架橋剤（Ｆ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The composition (III) for resin layer formation and the crosslinking agent (F) contained in the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination and ratio thereof Is optional.
　架橋剤（Ｆ）を用いる場合、樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムにおいて、架橋剤（Ｆ）の含有量は、重合体成分（Ａ）の含有量１００質量部に対して、０．０１～２０質量部であることが好ましく、０．１～１０質量部であることがより好ましく、０．５～５質量部であることが特に好ましい。架橋剤（Ｆ）の前記含有量が前記下限値以上であることで、架橋剤（Ｆ）を用いたことによる効果がより顕著に得られる。また、架橋剤（Ｆ）の前記含有量が前記上限値以下であることで、架橋剤（Ｆ）の過剰使用が抑制される。 When using a crosslinking agent (F), in the composition (III) for resin layer formation and the thermosetting resin film, the content of the crosslinking agent (F) is 100 parts by mass of the content of the polymer component (A) The amount is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass. The effect by using a crosslinking agent (F) is acquired more notably by the said content of a crosslinking agent (F) being more than the said lower limit. Moreover, the excess use of a crosslinking agent (F) is suppressed because the said content of a crosslinking agent (F) is below the said upper limit.
［エネルギー線硬化性樹脂（Ｇ）］
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムは、エネルギー線硬化性樹脂（Ｇ）を含有していてもよい。熱硬化性樹脂フィルムは、エネルギー線硬化性樹脂（Ｇ）を含有していることにより、エネルギー線の照射によって特性を変化させることができる。 [Energy ray curable resin (G)]
The composition for resin layer formation (III) and the thermosetting resin film may contain an energy ray curable resin (G). A thermosetting resin film can change a characteristic by irradiation of an energy ray by containing energy ray curable resin (G).
　エネルギー線硬化性樹脂（Ｇ）は、エネルギー線硬化性化合物を重合（硬化）して得られたものである。
　前記エネルギー線硬化性化合物としては、例えば、分子内に少なくとも１個の重合性二重結合を有する化合物が挙げられ、（メタ）アクリロイル基を有するアクリレート系化合物が好ましい。 The energy ray-curable resin (G) is obtained by polymerizing (curing) an energy ray-curable compound.
Examples of the energy ray curable compound include a compound having at least one polymerizable double bond in the molecule, and an acrylate compound having a (meth) acryloyl group is preferable.
　前記アクリレート系化合物としては、例えば、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、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリ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－ブチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート等の鎖状脂肪族骨格含有（メタ）アクリレート；ジシクロペンタニルジ（メタ）アクリレート等の環状脂肪族骨格含有（メタ）アクリレート；ポリエチレングリコールジ（メタ）アクリレート等のポリアルキレングリコール（メタ）アクリレート；オリゴエステル（メタ）アクリレート；ウレタン（メタ）アクリレートオリゴマー；エポキシ変性（メタ）アクリレート；前記ポリアルキレングリコール（メタ）アクリレート以外のポリエーテル（メタ）アクリレート；イタコン酸オリゴマー等が挙げられる。 Examples of the acrylate compound include trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol monohydroxy penta ( Linear aliphatic skeleton-containing (meth) acrylates such as meta) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; Cycloaliphatic skeleton-containing (meth) acrylates such as cyclopentanyl di (meth) acrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate Oligoester (meth) acrylate; urethane (meth) acrylate oligomer, epoxy-modified (meth) acrylate; the polyalkylene glycol (meth) Polyether (meth) acrylates other than the acrylates; itaconic acid oligomer, and the like.
　前記エネルギー線硬化性化合物の重量平均分子量は、１００～３００００であることが好ましく、３００～１００００であることがより好ましい。 The weight average molecular weight of the energy ray curable compound is preferably 100 to 30,000, and more preferably 300 to 10,000.
　重合に用いる前記エネルギー線硬化性化合物は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The energy ray-curable compound used for the polymerization may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムが含有するエネルギー線硬化性樹脂（Ｇ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The energy ray curable resin (G) contained in the resin layer forming composition (III) and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, Combinations and ratios can be selected arbitrarily.
　エネルギー線硬化性樹脂（Ｇ）を用いる場合、樹脂層形成用組成物（ＩＩＩ）において、樹脂層形成用組成物（ＩＩＩ）の総質量に対する、エネルギー線硬化性樹脂（Ｇ）の含有量の割合は、１～９５質量％であることが好ましく、５～９０質量％であることがより好ましく、１０～８５質量％であることが特に好ましい。 In the case of using the energy ray-curable resin (G), in the composition (III) for forming a resin layer, the ratio of the content of the energy ray-curable resin (G) to the total mass of the composition (III) for forming a resin layer Is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass.
［光重合開始剤（Ｈ）］
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムは、エネルギー線硬化性樹脂（Ｇ）を含有する場合、エネルギー線硬化性樹脂（Ｇ）の重合反応を効率よく進めるために、光重合開始剤（Ｈ）を含有していてもよい。 [Photoinitiator (H)]
When the composition for forming a resin layer (III) and the thermosetting resin film contain an energy ray-curable resin (G), photopolymerization is performed to efficiently promote the polymerization reaction of the energy ray-curable resin (G). You may contain the initiator (H).
　樹脂層形成用組成物（ＩＩＩ）における光重合開始剤（Ｈ）としては、例えば、ベンゾイン、ベンゾインメチルエーテル、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、ベンゾインイソブチルエーテル、ベンゾイン安息香酸、ベンゾイン安息香酸メチル、ベンゾインジメチルケタール等のベンゾイン化合物；アセトフェノン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン等のアセトフェノン化合物；ビス（２，４，６－トリメチルベンゾイル）フェニルフォスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド等のアシルフォスフィンオキサイド化合物；ベンジルフェニルスルフィド、テトラメチルチウラムモノスルフィド等のスルフィド化合物；１－ヒドロキシシクロヘキシルフェニルケトン等のα－ケトール化合物；アゾビスイソブチロニトリル等のアゾ化合物；チタノセン等のチタノセン化合物；チオキサント、２，４－ジエチルチオキサントン等のチオキサントン化合物；パーオキサイド化合物；ジアセチル等のジケトン化合物；ベンジル；ジベンジル；ベンゾフェノン；１，２－ジフェニルメタン；２－ヒドロキシ－２－メチル－１－［４－（１－メチルビニル）フェニル］プロパノン；２－クロロアントラキノン等が挙げられる。
　また、光重合開始剤（Ｈ）としては、例えば、１－クロロアントラキノン等のキノン化合物；アミン等の光増感剤等を用いることもできる。 Examples of the photopolymerization initiator (H) in the composition (III) for forming a resin layer include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin benzoate Benzoin compounds such as dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one; Acyl phosphine oxide compounds such as 2,4,6-trimethyl benzoyl) phenyl phosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; benzyl phenyl sulfide, tetramethyl Sulfide compounds such as uram monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthate and 2,4-diethylthioxanthone Peroxide compounds; Diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone Etc.
Further, as the photopolymerization initiator (H), for example, quinone compounds such as 1-chloroanthraquinone and the like; photosensitizers such as amine and the like can also be used.
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムが含有する光重合開始剤（Ｈ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The composition (III) for forming a resin layer and the photopolymerization initiator (H) contained in the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination thereof And the ratio can be selected arbitrarily.
　光重合開始剤（Ｈ）を用いる場合、樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムにおいて、光重合開始剤（Ｈ）の含有量は、エネルギー線硬化性樹脂（Ｇ）の含有量１００質量部に対して、０．１～２０質量部であることが好ましく、１～１０質量部であることがより好ましく、２～５質量部であることが特に好ましい。 When a photopolymerization initiator (H) is used, the content of the photopolymerization initiator (H) in the resin layer-forming composition (III) and the thermosetting resin film is the content of the energy ray-curable resin (G) The amount is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass with respect to 100 parts by mass.
［着色剤（Ｉ）］
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムは、着色剤（Ｉ）を含有していてもよい。着色剤（Ｉ）は、例えば、熱硬化性樹脂フィルム及び第１保護膜に、適切な光線透過率を付与するための成分である。
　着色剤（Ｉ）は、公知のものでよく、例えば、染料及び顔料のいずれであってもよい。
　例えば、染料は、酸性染料、反応染料、直接染料、分散染料及びカチオン染料等のいずれであってもよい。 [Colorant (I)]
The composition for forming a resin layer (III) and the thermosetting resin film may contain a colorant (I). The colorant (I) is, for example, a component for imparting an appropriate light transmittance to the thermosetting resin film and the first protective film.
The colorant (I) may be known and may be, for example, any of a dye and a pigment.
For example, the dyes may be any of acid dyes, reactive dyes, direct dyes, disperse dyes, cationic dyes and the like.
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムが含有する着色剤（Ｉ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The colorant (I) contained in the resin layer-forming composition (III) and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination and ratio thereof Is optional.
　着色剤（Ｉ）を用いる場合、樹脂層形成用組成物（ＩＩＩ）の着色剤（Ｉ）の含有量は、熱硬化性樹脂フィルムの可視光線透過率及び赤外線透過率が目的の値となるように適宜調節すればよく、特に限定されない。例えば、前記着色剤（Ｉ）の含有量は、着色剤（Ｉ）の種類や、２種以上の着色剤（Ｉ）を併用する場合には、これら着色剤（Ｉ）の組み合わせ等に応じて、適宜調節すればよい。 When the coloring agent (I) is used, the content of the coloring agent (I) of the composition (III) for forming a resin layer is such that the visible light transmittance and the infrared transmittance of the thermosetting resin film become the target values. No particular limitation is imposed on the adjustment. For example, the content of the coloring agent (I) depends on the type of the coloring agent (I) or, in the case of using two or more kinds of coloring agents (I) in combination, depending on the combination of the coloring agent (I), etc. And may be adjusted as appropriate.
　着色剤（Ｉ）を用いる場合、通常は、樹脂層形成用組成物（ＩＩＩ）において、溶媒以外の全ての成分の総含有量に対する、着色剤（Ｉ）の含有量の割合（すなわち、熱硬化性樹脂フィルムにおける、熱硬化性樹脂フィルムの総質量に対する、着色剤（Ｉ）の含有量の割合）は、０．０１～１０質量％であることが好ましい。 In the case of using the colorant (I), in general, the ratio of the content of the colorant (I) to the total content of all components other than the solvent in the resin layer-forming composition (III) (that is, heat curing The ratio of the content of the colorant (I) to the total mass of the thermosetting resin film in the transparent resin film is preferably 0.01 to 10% by mass.
［汎用添加剤（Ｊ）］
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムは、本発明の効果を損なわない範囲内において、汎用添加剤（Ｊ）を含有していてもよい。
　汎用添加剤（Ｊ）は、公知のものでよく、目的に応じて任意に選択でき、特に限定されないが、好ましいものとしては、例えば、可塑剤、帯電防止剤、酸化防止剤、ゲッタリング剤等が挙げられる。 [General purpose additive (J)]
The composition for forming a resin layer (III) and the thermosetting resin film may contain a general-purpose additive (J) within the range not impairing the effects of the present invention.
The general-purpose additive (J) may be a known one, can be optionally selected according to the purpose, and is not particularly limited. Preferred examples thereof include a plasticizer, an antistatic agent, an antioxidant, a gettering agent, etc. Can be mentioned.
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムが含有する汎用添加剤（Ｊ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムの汎用添加剤（Ｊ）の含有量は、特に限定されず、目的に応じて適宜選択すればよい。 The general-purpose additive (J) contained in the resin layer-forming composition (III) and the thermosetting resin film may be only one type, or two or more types, and in the case of two or more types, a combination thereof and The ratio can be selected arbitrarily.
The content of the general-purpose additive (J) in the composition for forming a resin layer (III) and the thermosetting resin film is not particularly limited, and may be appropriately selected depending on the purpose.
［溶媒］
　樹脂層形成用組成物（ＩＩＩ）は、さらに溶媒を含有することが好ましい。溶媒を含有する樹脂層形成用組成物（ＩＩＩ）は、取り扱い性が良好となる。
　前記溶媒は特に限定されないが、好ましいものとしては、例えば、トルエン、キシレン等の炭化水素；メタノール、エタノール、２－プロパノール、イソブチルアルコール（２－メチルプロパン－１－オール）、１－ブタノール等のアルコール；酢酸エチル等のエステル；アセトン、メチルエチルケトン等のケトン；テトラヒドロフラン等のエーテル；ジメチルホルムアミド、Ｎ－メチルピロリドン等のアミド（アミド結合を有する化合物）等が挙げられる。
　樹脂層形成用組成物（ＩＩＩ）が含有する溶媒は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 [solvent]
The composition for forming a resin layer (III) preferably further contains a solvent. The composition for forming a resin layer (III) containing a solvent has good handleability.
The solvent is not particularly limited, but preferred examples thereof include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), 1-butanol and the like Esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methyl pyrrolidone.
The solvent contained in the resin layer-forming composition (III) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
　樹脂層形成用組成物（ＩＩＩ）が含有する溶媒は、樹脂層形成用組成物（ＩＩＩ）中の含有成分をより均一に混合できる点から、メチルエチルケトン等であることが好ましい。 The solvent contained in the resin layer-forming composition (III) is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the resin layer-forming composition (III) can be mixed more uniformly.
　樹脂層形成用組成物（ＩＩＩ）の溶媒の含有量は、特に限定されず、例えば、溶媒以外の成分の種類に応じて適宜選択すればよい。 The content of the solvent in the composition for forming a resin layer (III) is not particularly limited, and may be appropriately selected, for example, according to the types of components other than the solvent.
　樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムは、重合体成分（Ａ）及び熱硬化性成分（Ｂ）を含有し、重合体成分（Ａ）としてポリビニルアセタールを含有し、かつエポキシ樹脂（Ｂ１）として液状のものを含有することが好ましく、これら成分以外に、さらに、硬化促進剤（Ｃ）及び充填材（Ｄ）を含有するものがより好ましい。そして、この場合の充填材（Ｄ）は、上述の平均粒径を有することが好ましい。このような樹脂層形成用組成物（ＩＩＩ）及び熱硬化性樹脂フィルムを用いることで、バンプの頭頂部において、第１保護膜残留物の残存を抑制する効果がより高くなる。 The composition (III) for forming a resin layer and the thermosetting resin film contain the polymer component (A) and the thermosetting component (B), contain polyvinyl acetal as the polymer component (A), and are epoxy It is preferable to contain a liquid thing as resin (B1), and what further contains a hardening accelerator (C) and a filler (D) other than these components is more preferable. And it is preferable that the filler (D) in this case has the above-mentioned average particle diameter. By using such a composition for resin layer formation (III) and a thermosetting resin film, the effect of suppressing the remaining of the first protective film residue becomes higher at the top of the bump.
　樹脂層形成用組成物（ＩＩＩ）で好ましいものの一実施形態としては、例えば、ポリビニルアセタールである重合体成分（Ａ）と、液状のエポキシ樹脂（Ｂ１）と、熱硬化剤（Ｂ２）と、硬化促進剤（Ｃ）と、充填材（Ｄ）と、を含有し、樹脂層形成用組成物（ＩＩＩ）において、前記エポキシ樹脂（Ｂ１）と熱硬化剤（Ｂ２）との総含有量が、前記重合体成分（Ａ）の含有量１００質量部に対して、６００～１０００質量部であり、かつ、硬化促進剤（Ｃ）の含有量が、前記エポキシ樹脂（Ｂ１）と熱硬化剤（Ｂ２）との総含有量１００質量部に対して、０．１～５質量部であり、樹脂層形成用組成物（ＩＩＩ）において、溶媒以外の全ての成分の総含有量に対する、充填材（Ｄ）の含有量の割合が、３～３０質量％であり、充填材（Ｄ）の平均粒径が６μｍ以下であるものが挙げられる。 As one embodiment preferred as the composition (III) for forming a resin layer, for example, a polymer component (A) which is a polyvinyl acetal, a liquid epoxy resin (B1), a thermosetting agent (B2), and curing It contains an accelerator (C) and a filler (D), and in the composition (III) for forming a resin layer, the total content of the epoxy resin (B1) and the thermosetting agent (B2) is the above-mentioned content. It is 600 to 1000 parts by mass with respect to 100 parts by mass of the polymer component (A), and the content of the curing accelerator (C) is the epoxy resin (B1) and the thermosetting agent (B2) And 0.1 to 5 parts by mass with respect to 100 parts by mass of the filler, and the filler (D) with respect to the total content of all the components other than the solvent in the composition for forming a resin layer (III) The content ratio of the filler is 3 to 30% by mass, and the filler (D The average particle diameter of include those at 6μm or less.
　樹脂層形成用組成物（ＩＩＩ）でより好ましいものの一実施形態としては、例えば、ポリビニルアセタールである重合体成分（Ａ）と、液状のエポキシ樹脂（Ｂ１）と、熱硬化剤（Ｂ２）と、硬化促進剤（Ｃ）と、充填材（Ｄ）と、を含有し、前記ポリビニルアセタールの重量平均分子量が４００００以下であり、前記エポキシ樹脂（Ｂ１）の重量平均分子量が１００００以下であり、樹脂層形成用組成物（ＩＩＩ）において、前記エポキシ樹脂（Ｂ１）と熱硬化剤（Ｂ２）との総含有量が、前記重合体成分（Ａ）の含有量１００質量部に対して、６００～１０００質量部であり、かつ、硬化促進剤（Ｃ）の含有量が、前記エポキシ樹脂（Ｂ１）と熱硬化剤（Ｂ２）との総含有量１００質量部に対して、０．１～５質量部であり、樹脂層形成用組成物（ＩＩＩ）において、溶媒以外の全ての成分の総含有量に対する、充填材（Ｄ）の含有量の割合が、５～１５質量％であり、充填材（Ｄ）の平均粒径が２μｍ以下であるものが挙げられる。 As one embodiment more preferable as the composition (III) for forming a resin layer, for example, a polymer component (A) which is a polyvinyl acetal, a liquid epoxy resin (B1), and a thermosetting agent (B2), A curing accelerator (C) and a filler (D), the weight average molecular weight of the polyvinyl acetal is 40000 or less, the weight average molecular weight of the epoxy resin (B1) is 10000 or less, and a resin layer In the composition for formation (III), the total content of the epoxy resin (B1) and the thermosetting agent (B2) is 600 to 1000 parts by mass with respect to 100 parts by mass of the content of the polymer component (A). The content of the curing accelerator (C) is 0.1 to 5 parts by mass with respect to 100 parts by mass of the total content of the epoxy resin (B1) and the thermosetting agent (B2). Yes, resin layer type In the composition (III), the ratio of the content of the filler (D) to the total content of all the components other than the solvent is 5 to 15% by mass, and the average particle diameter of the filler (D) is What is 2 micrometers or less is mentioned.
◎熱硬化性樹脂フィルム形成用組成物の製造方法
　樹脂層形成用組成物（ＩＩＩ）等の熱硬化性樹脂フィルム形成用組成物は、これを構成するための各成分を配合することで得られる。
　各成分の配合時における添加順序は特に限定されず、２種以上の成分を同時に添加してもよい。
　溶媒を用いる場合には、溶媒を溶媒以外のいずれかの配合成分と混合してこの配合成分を予め希釈しておくことで用いてもよいし、溶媒以外のいずれかの配合成分を予め希釈しておくことなく、溶媒をこれら配合成分と混合することで用いてもよい。
　配合時に各成分を混合する方法は特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法；ミキサーを用いて混合する方法；超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。
　各成分の添加及び混合時の温度並びに時間は、各配合成分が劣化しない限り特に限定されず、適宜調節すればよいが、温度は１５～３０℃であることが好ましい。 製造 Method of producing the composition for forming a thermosetting resin film The composition for forming a thermosetting resin film such as the composition for forming a resin layer (III) can be obtained by blending the respective components for constituting the composition .
There is no particular limitation on the order of addition of each component at the time of blending, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting this compounding component in advance, or by previously diluting any compounding component other than the solvent A solvent may be used by mixing with these compounding ingredients without storage.
The method of mixing each component at the time of compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer; a method of adding ultrasonic waves and mixing, etc. It may be selected as appropriate.
The temperature and time of addition and mixing of the respective components are not particularly limited as long as the respective blended components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.
◎エネルギー線硬化性樹脂フィルム形成用組成物
○樹脂層形成用組成物（ＩＶ）
　エネルギー線硬化性樹脂フィルム形成用組成物としては、例えば、エネルギー線硬化性成分（ａ）を含有するエネルギー線硬化性樹脂フィルム形成用組成物（ＩＶ）（本明細書においては、単に「樹脂層形成用組成物（ＩＶ）」と略記することがある）等が挙げられる。 組成 Composition for forming energy ray curable resin film ○ Composition for forming resin layer (IV)
As the composition for forming an energy ray-curable resin film, for example, a composition for forming an energy ray-curable resin film (IV) containing an energy ray-curable component (a) (in the present specification, simply “resin layer And the like, which may be abbreviated as “forming composition (IV)”.
［エネルギー線硬化性成分（ａ）］
　エネルギー線硬化性成分（ａ）は、エネルギー線の照射によって硬化する成分であり、エネルギー線硬化性樹脂フィルムに造膜性や、可撓性等を付与するための成分でもある。
　エネルギー線硬化性成分（ａ）としては、例えば、エネルギー線硬化性基を有する、重量平均分子量が８００００～２００００００の重合体（ａ１）、及びエネルギー線硬化性基を有する、分子量が１００～８００００の化合物（ａ２）が挙げられる。前記重合体（ａ１）は、その少なくとも一部が架橋剤によって架橋されたものであってもよいし、架橋されていないものであってもよい。 [Energy ray curable component (a)]
The energy ray curable component (a) is a component which is cured by irradiation of energy rays, and is also a component for imparting film forming property, flexibility and the like to the energy ray curable resin film.
The energy ray curable component (a) includes, for example, an energy ray curable group, a polymer (a1) having a weight average molecular weight of 80000 to 2,000,000, and an energy ray curable group having a molecular weight of 100 to 80,000. Compound (a2) is mentioned. The polymer (a1) may be at least partially crosslinked by a crosslinking agent, or may be non-crosslinked.
　エネルギー線硬化性基を有する、重量平均分子量が８００００～２００００００の重合体（ａ１）としては、例えば、他の化合物が有する基と反応可能な官能基を有するアクリル系重合体（ａ１１）と、前記官能基と反応する基、及びエネルギー線硬化性二重結合等のエネルギー線硬化性基を有するエネルギー線硬化性化合物（ａ１２）と、が重合してなるアクリル系樹脂（ａ１－１）が挙げられる。 Examples of the polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000 include an acrylic polymer (a11) having a functional group capable of reacting with a group possessed by another compound, Acrylic resin (a1-1) formed by polymerizing an energy ray curable compound (a12) having a group reactive with a functional group and an energy ray curable group such as an energy ray curable double bond .
　他の化合物が有する基と反応可能な前記官能基としては、例えば、水酸基、カルボキシ基、アミノ基、置換アミノ基（アミノ基の１個又は２個の水素原子が水素原子以外の基で置換されてなる基）、エポキシ基等が挙げられる。ただし、半導体ウエハや半導体チップ等の回路の腐食を防止するという点では、前記官能基はカルボキシ基以外の基であることが好ましい。
　これらの中でも、前記官能基は、水酸基であることが好ましい。 Examples of the functional group capable of reacting with a group possessed by another compound include, for example, a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom Groups), epoxy groups and the like. However, in terms of preventing corrosion of circuits such as semiconductor wafers and semiconductor chips, the functional group is preferably a group other than a carboxy group.
Among these, the functional group is preferably a hydroxyl group.
　前記官能基を有するアクリル系重合体（ａ１１）としては、例えば、前記官能基を有するアクリル系モノマーと、前記官能基を有しないアクリル系モノマーと、が共重合してなるものが挙げられ、これらモノマー以外に、さらにアクリル系モノマー以外のモノマー（非アクリル系モノマー）が共重合したものであってもよい。
　また、前記アクリル系重合体（ａ１１）は、ランダム共重合体であってもよいし、ブロック共重合体であってもよい。 Examples of the acrylic polymer (a11) having a functional group include those obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer having no functional group. In addition to the monomers, monomers (non-acrylic monomers) other than acrylic monomers may be copolymerized.
The acrylic polymer (a11) may be a random copolymer or a block copolymer.
　前記アクリル系重合体（ａ１１）において、前記官能基を有するアクリル系モノマー、前記官能基を有しないアクリル系モノマー、及び非アクリル系モノマーは、いずれも１種を単独で用いてもよいし、２種以上を併用してもよく、２種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。 In the acrylic polymer (a11), the acrylic monomer having the functional group, the acrylic monomer having no functional group, and the non-acrylic monomer may be used alone or in combination of two or more. More than one species may be used in combination, and when two or more species are used in combination, their combination and ratio can be arbitrarily selected.
　前記エネルギー線硬化性化合物（ａ１２）は、前記アクリル系重合体（ａ１１）が有する官能基と反応可能な基として、イソシアネート基、エポキシ基及びカルボキシ基からなる群より選択される１種又は２種以上を有するものが好ましく、前記基としてイソシアネート基を有するものがより好ましい。前記エネルギー線硬化性化合物（ａ１２）は、例えば、前記基としてイソシアネート基を有する場合、このイソシアネート基が、前記官能基として水酸基を有するアクリル系重合体（ａ１１）のこの水酸基と容易に反応する。 The energy ray curable compound (a12) is one or two selected from the group consisting of an isocyanate group, an epoxy group and a carboxy group as a group capable of reacting with the functional group possessed by the acrylic polymer (a11) What has the above is preferable, and what has an isocyanate group as said group is more preferable. When the energy beam curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.
　エネルギー線硬化性基を有する、分子量が１００～８００００の化合物（ａ２）中の前記エネルギー線硬化性基としては、エネルギー線硬化性二重結合を含む基が挙げられ、好ましいものとしては、（メタ）アクリロイル基、ビニル基等が挙げられる。 Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80,000 include a group containing an energy ray-curable double bond, and preferred examples thereof Acryloyl group, a vinyl group etc. are mentioned.
［エネルギー線硬化性基を有しない重合体（ｂ）］
　樹脂層形成用組成物（ＩＶ）及びエネルギー線硬化性樹脂フィルムは、前記エネルギー線硬化性成分（ａ）として前記化合物（ａ２）を含有する場合、さらにエネルギー線硬化性基を有しない重合体（ｂ）も含有することが好ましい。
　前記重合体（ｂ）は、その少なくとも一部が架橋剤によって架橋されたものであってもよいし、架橋されていないものであってもよい。 [Polymer having no energy ray curable group (b)]
When the composition for forming a resin layer (IV) and the energy ray-curable resin film contain the compound (a2) as the energy ray-curable component (a), a polymer having no energy ray-curable group ( It is preferable to also contain b).
The polymer (b) may be at least partially crosslinked by a crosslinking agent, or may be non-crosslinked.
　エネルギー線硬化性基を有しない重合体（ｂ）としては、例えば、アクリル系重合体、フェノキシ樹脂、ウレタン樹脂、ポリエステル、ゴム系樹脂、アクリルウレタン樹脂等が挙げられる。
　これらの中でも、前記重合体（ｂ）は、アクリル系重合体（本明細書においては、「アクリル系重合体（ｂ－１）」と称することがある）であることが好ましい。 Examples of the polymer (b) having no energy ray curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, acrylic urethane resins, and the like.
Among these, the polymer (b) is preferably an acrylic polymer (sometimes referred to as “acrylic polymer (b-1)” in the present specification).
　樹脂層形成用組成物（ＩＶ）としては、前記重合体（ａ１）及び前記化合物（ａ２）のいずれか一方又は両方を含有するものが挙げられる。そして、樹脂層形成用組成物（ＩＶ）は、前記化合物（ａ２）を含有する場合、さらにエネルギー線硬化性基を有しない重合体（ｂ）も含有することが好ましく、この場合、さらに前記重合体（ａ１）を含有することも好ましい。また、樹脂層形成用組成物（ＩＶ）は、前記化合物（ａ２）を含有せず、前記重合体（ａ１）、及びエネルギー線硬化性基を有しない重合体（ｂ）をともに含有していてもよい。 Examples of the composition (IV) for forming a resin layer include those containing one or both of the polymer (a1) and the compound (a2). And when the composition (IV) for resin layer formation contains the said compound (a2), it is preferable to also contain the polymer (b) which does not have an energy ray curable group further, and in this case, the said weight is further added. It is also preferable to contain a united body (a1). In addition, the composition for forming a resin layer (IV) contains neither the compound (a2) but the polymer (a1) and the polymer (b) having no energy ray curable group. It is also good.
　樹脂層形成用組成物（ＩＶ）において、前記エネルギー線硬化性成分（ａ）、及びエネルギー線硬化性基を有しない重合体（ｂ）は、それぞれ、１種を単独で用いてもよいし、２種以上を併用してもよく、２種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。 In the composition (IV) for forming a resin layer, the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group may be used alone, respectively. Two or more types may be used in combination, and when two or more types are used in combination, their combination and ratio can be arbitrarily selected.
　樹脂層形成用組成物（ＩＶ）が、前記重合体（ａ１）、前記化合物（ａ２）及びエネルギー線硬化性基を有しない重合体（ｂ）を含有する場合、樹脂層形成用組成物（ＩＶ）において、前記化合物（ａ２）の含有量は、前記重合体（ａ１）及びエネルギー線硬化性基を有しない重合体（ｂ）の総含有量１００質量部に対して、１０～４００質量部であることが好ましい。 When the composition for resin layer formation (IV) contains the polymer (a1), the compound (a2) and the polymer (b) having no energy ray curable group, the composition for resin layer formation (IV) In the above, the content of the compound (a2) is 10 to 400 parts by mass with respect to 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray curable group. Is preferred.
　樹脂層形成用組成物（ＩＶ）において、溶媒以外の成分の総含有量に対する、前記エネルギー線硬化性成分（ａ）及びエネルギー線硬化性基を有しない重合体（ｂ）の合計含有量の割合（すなわち、エネルギー線硬化性樹脂フィルムにおける、エネルギー線硬化性樹脂フィルムの総質量に対する、前記エネルギー線硬化性成分（ａ）及びエネルギー線硬化性基を有しない重合体（ｂ）の合計含有量の割合）は、５～９０質量％であることが好ましい。 In the composition (IV) for forming a resin layer, the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (Ie, the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group in the energy ray-curable resin film relative to the total mass of the energy ray-curable resin film The proportion) is preferably 5 to 90% by mass.
　樹脂層形成用組成物（ＩＶ）は、前記エネルギー線硬化性成分以外に、目的に応じて、熱硬化性成分、光重合開始剤、充填材、カップリング剤、架橋剤、着色剤、汎用添加剤及び溶媒からなる群より選択される１種又は２種以上を含有していてもよい。例えば、前記エネルギー線硬化性成分及び熱硬化性成分を含有する樹脂層形成用組成物（ＩＶ）を用いることにより、形成されるエネルギー線硬化性樹脂フィルムは、加熱によって被着体に対する接着力が向上し、このエネルギー線硬化性樹脂フィルムから形成された第１保護膜の強度も向上する。 The composition for forming a resin layer (IV) may contain, according to the purpose, a thermosetting component, a photopolymerization initiator, a filler, a coupling agent, a crosslinking agent, a coloring agent, and a general-purpose addition, in addition to the energy ray curable component. It may contain one or more selected from the group consisting of an agent and a solvent. For example, by using the composition for forming a resin layer (IV) containing the energy ray-curable component and the thermosetting component, the energy ray-curable resin film formed has an adhesive force to an adherend by heating. The strength of the first protective film formed from the energy ray-curable resin film is also improved.
　樹脂層形成用組成物（ＩＶ）における前記熱硬化性成分、光重合開始剤、充填材、カップリング剤、架橋剤、着色剤、汎用添加剤及び溶媒としては、それぞれ、樹脂層形成用組成物（ＩＩＩ）における熱硬化性成分（Ｂ）、光重合開始剤（Ｈ）、充填材（Ｄ）、カップリング剤（Ｅ）、架橋剤（Ｆ）、着色剤（Ｉ）、汎用添加剤（Ｊ）及び溶媒と同じものが挙げられる。 As the thermosetting component, the photopolymerization initiator, the filler, the coupling agent, the crosslinking agent, the colorant, the general-purpose additive and the solvent in the composition (IV) for forming a resin layer, a composition for forming a resin layer (III) thermosetting component (B), photopolymerization initiator (H), filler (D), coupling agent (E), crosslinking agent (F), colorant (I), general purpose additive (J And the same as the solvent.
　樹脂層形成用組成物（ＩＶ）において、前記熱硬化性成分、光重合開始剤、充填材、カップリング剤、架橋剤、着色剤、汎用添加剤及び溶媒は、それぞれ、１種を単独で用いてもよいし、２種以上を併用してもよく、２種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。
　樹脂層形成用組成物（ＩＶ）における前記熱硬化性成分、光重合開始剤、充填材、カップリング剤、架橋剤、着色剤、汎用添加剤及び溶媒の含有量は、目的に応じて適宜調節すればよく、特に限定されない。 In the composition (IV) for forming a resin layer, the thermosetting component, the photopolymerization initiator, the filler, the coupling agent, the crosslinking agent, the crosslinking agent, the coloring agent, the general-purpose additive and the solvent are each used alone. When using together 2 or more types and 2 or more types together, those combinations and ratios can be selected arbitrarily.
The content of the thermosetting component, the photopolymerization initiator, the filler, the coupling agent, the crosslinking agent, the coloring agent, the general-purpose additive and the solvent in the composition (IV) for forming a resin layer is appropriately adjusted according to the purpose. There is no particular limitation as long as the
◎エネルギー線硬化性樹脂フィルム形成用組成物の製造方法
　樹脂層形成用組成物（ＩＶ）等のエネルギー線硬化性樹脂フィルム形成用組成物は、これを構成するための各成分を配合することで得られる。
　各成分の配合時における添加順序は特に限定されず、２種以上の成分を同時に添加してもよい。
　溶媒を用いる場合には、溶媒を溶媒以外のいずれかの配合成分と混合してこの配合成分を予め希釈しておくことで用いてもよいし、溶媒以外のいずれかの配合成分を予め希釈しておくことなく、溶媒をこれら配合成分と混合することで用いてもよい。
　配合時に各成分を混合する方法は特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法；ミキサーを用いて混合する方法；超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。
　各成分の添加及び混合時の温度並びに時間は、各配合成分が劣化しない限り特に限定されず、適宜調節すればよいが、温度は１５～３０℃であることが好ましい。 製造 Method of producing the composition for forming an energy ray-curable resin film The composition for forming an energy ray-curable resin film, such as the composition for forming a resin layer (IV), is obtained by blending the components for constituting the composition can get.
There is no particular limitation on the order of addition of each component at the time of blending, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting this compounding component in advance, or by previously diluting any compounding component other than the solvent A solvent may be used by mixing with these compounding ingredients without storage.
The method of mixing each component at the time of compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer; a method of adding ultrasonic waves and mixing, etc. It may be selected as appropriate.
The temperature and time of addition and mixing of the respective components are not particularly limited as long as the respective blended components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.
◇第１保護膜付き半導体チップの製造方法
　本発明の第１保護膜付き半導体チップの製造方法は、上述の第１保護膜付き半導体チップの製造方法であって、半導体ウエハのバンプを有する面に、硬化性樹脂フィルムを貼付する工程（本明細書においては、「貼付工程」と略記することがある）と、貼付後の前記硬化性樹脂フィルムを硬化させることにより、第１保護膜を形成する工程（本明細書においては、「第１保護膜形成工程」と略記することがある）と、前記半導体ウエハを分割することにより、半導体チップを得る工程（本明細書においては、「分割工程」と略記することがある）と、を有し、前記硬化性樹脂フィルムを貼付する工程において、前記Ｓ（Ｃ）／Ｓ（Ｓｎ）の値が０．３２以下となるように、前記バンプの頭頂部を前記硬化性樹脂フィルムから突出させるか、又は、前記硬化性樹脂フィルムを貼付する工程の後に、さらに、前記Ｓ（Ｃ）／Ｓ（Ｓｎ）の値が０．３２以下となるように、前記バンプ上の残留物の量を低減する工程（本明細書においては、「残留物低減工程」と略記することがある）を有する。
　以下、図面を参照しながら、前記製造方法について説明する。 A method of manufacturing a semiconductor chip with a first protective film The method of manufacturing a semiconductor chip with a first protective film of the present invention is a method of manufacturing a semiconductor chip with a first protective film described above, and the method of manufacturing the semiconductor chip with a first protective film Forming a first protective film by attaching a curable resin film (which may be abbreviated as "adhering step" in the present specification) and curing the curable resin film after application; A step (sometimes abbreviated "first protective film forming step" in the present specification) and a step of obtaining a semiconductor chip by dividing the semiconductor wafer (the "division step" in the present specification) In the step of attaching the curable resin film, the head of the bump such that the value of the S (C) / S (Sn) is 0.32 or less Above the top After the step of causing the curable resin film to protrude or attaching the curable resin film, the S (C) / S (Sn) value may be 0.32 or less on the bumps. Of reducing the amount of residue (sometimes abbreviated as "residue reduction step" in the present specification).
Hereinafter, the manufacturing method will be described with reference to the drawings.
　まず、図１に示す第１保護膜付き半導体チップの製造方法について、説明する。図５は、本実施形態を模式的に説明するための拡大断面図である。 First, a method of manufacturing the semiconductor chip with a first protective film shown in FIG. 1 will be described. FIG. 5 is an enlarged cross-sectional view for schematically describing the present embodiment.
＜貼付工程＞
　前記製造方法においては、まず、前記貼付工程を行い、図５（ａ）に示すように、半導体ウエハ９’のバンプ形成面９ａに、硬化性樹脂フィルム１３’を貼付する。本工程を行うことにより、硬化性樹脂フィルム１３’が、多数個存在するバンプ９１間に広がって、バンプ形成面９ａに密着するとともに、バンプ９１の表面９１ａ、特にバンプ形成面９ａの近傍部位の表面９１ａを覆って、バンプ９１を埋め込み、これらの領域を被覆している状態とすることができる。
　本工程においては、例えば、半導体ウエハ９’のバンプ９１の頭頂部９１０は、硬化性樹脂フィルム１３’を貫通して、硬化性樹脂フィルム１３’から突出する。 <Pasting process>
In the manufacturing method, first, the attaching process is performed, and as shown in FIG. 5A, the curable resin film 13 ′ is attached to the bump forming surface 9a of the semiconductor wafer 9 ′. By performing this step, the curable resin film 13 'spreads between the large number of bumps 91 and adheres to the bump forming surface 9a, and at the same time, the surface 91a of the bumps 91, particularly the vicinity of the bump forming surface 9a. It is possible to cover the surface 91 a and embed the bumps 91 so as to cover these areas.
In this process, for example, the top portion 910 of the bump 91 of the semiconductor wafer 9 ′ penetrates the curable resin film 13 ′ and protrudes from the curable resin film 13 ′.
　貼付工程においては、例えば、硬化性樹脂フィルム１３’を単独で用いてもよいが、ここに示すように、第１支持シート１０と、第１支持シート１０上に形成された硬化性樹脂フィルム１３’と、を備えて構成された、第１保護膜形成用シート１９１を用いることが好ましい。このような第１保護膜形成用シート１９１を用いることにより、硬化性樹脂フィルム１３’とバンプ形成面９ａとの間、並びに、硬化性樹脂フィルム１３’とバンプ９１の表面９１ａとの間、のいずれにおいても、空隙部の発生をより抑制できる。また最終的に、バンプ９１の頭頂部９１０において、第１保護膜残留物の残存を抑制する効果がより高くなる。 In the sticking step, for example, the curable resin film 13 ′ may be used alone, but as shown here, the first support sheet 10 and the curable resin film 13 formed on the first support sheet 10 It is preferable to use the first protective film forming sheet 191 configured to include '. By using such a sheet 191 for forming a first protective film, the space between the curable resin film 13 ′ and the bump formation surface 9 a and the space between the curable resin film 13 ′ and the surface 91 a of the bumps 91 In either case, the generation of the void can be further suppressed. Finally, the top portion 910 of the bump 91 has a higher effect of suppressing the remaining of the first protective film residue.
　貼付工程において、ここに示すような第１保護膜形成用シートを用いる場合には、第１保護膜形成用シート中の硬化性樹脂フィルムを半導体ウエハのバンプ形成面に貼付することにより、第１保護膜形成用シート自体を、半導体ウエハのバンプ形成面に貼付すればよい。
　なお、本明細書においては、ここに示すような、半導体ウエハのバンプ形成面に、第１保護膜形成用シートが貼付されて構成されたものを、「積層構造体（１）」と称することがある。図５においては、積層構造体（１）１０１として、半導体ウエハ９’のバンプ形成面９ａに、第１保護膜形成用シート１９１が貼付されて構成されたものを示している。 In the sticking step, when using a sheet for forming a first protective film as shown here, the first step is to attach the curable resin film in the sheet for forming a first protective film to the bump forming surface of the semiconductor wafer. The protective film forming sheet itself may be attached to the bump forming surface of the semiconductor wafer.
In the present specification, as shown here, a structure in which a sheet for forming a first protective film is attached to a bump forming surface of a semiconductor wafer is referred to as “laminated structure (1)”. There is. In FIG. 5, as the laminated structure (1) 101, the one in which the sheet 191 for forming a first protective film is attached to the bump formation surface 9a of the semiconductor wafer 9 ′ is shown.
　第１保護膜形成用シート１９１において、第１支持シート１０は、第１基材１１と、第１基材１１上に形成された緩衝層１２と、を備えて構成されている。すなわち、第１保護膜形成用シート１９１は、第１基材１１、緩衝層１２及び硬化性樹脂フィルム１３’がこの順に、これらの厚さ方向において積層されて、構成されている。
　図６は、第１保護膜形成用シート１９１を模式的に示す拡大断面図である。 In the first protective film-forming sheet 191, the first support sheet 10 is configured to include the first base 11 and the buffer layer 12 formed on the first base 11. That is, the first protective film-forming sheet 191 is configured by laminating the first base material 11, the buffer layer 12, and the curable resin film 13 'in this order in the thickness direction.
FIG. 6 is an enlarged cross-sectional view schematically showing the first protective film formation sheet 191. As shown in FIG.
　第１支持シート１０としては、公知のものを用いることができる。 As the first support sheet 10, a known one can be used.
　第１基材１１は、シート状又はフィルム状であり、その構成材料としては、例えば、各種樹脂が挙げられる。
　前記樹脂としては、例えば、低密度ポリエチレン（ＬＤＰＥ）、直鎖低密度ポリエチレン（ＬＬＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）等のポリエチレン；ポリプロピレン、ポリブテン、ポリブタジエン、ポリメチルペンテン、ノルボルネン樹脂等のポリエチレン以外のポリオレフィン；エチレン－酢酸ビニル共重合体、エチレン－（メタ）アクリル酸共重合体、エチレン－（メタ）アクリル酸エステル共重合体、エチレン－ノルボルネン共重合体等のエチレン系共重合体（モノマーとしてエチレンを用いて得られた共重合体）；ポリ塩化ビニル、塩化ビニル共重合体等の塩化ビニル系樹脂（モノマーとして塩化ビニルを用いて得られた樹脂）；ポリスチレン；ポリシクロオレフィン；ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリエチレンイソフタレート、ポリエチレン－２，６－ナフタレンジカルボキシレート、すべての構成単位が芳香族環式基を有する全芳香族ポリエステル等のポリエステル；２種以上の前記ポリエステルの共重合体；ポリ（メタ）アクリル酸エステル；ポリウレタン；ポリウレタンアクリレート；ポリイミド；ポリアミド；ポリカーボネート；フッ素樹脂；ポリアセタール；変性ポリフェニレンオキシド；ポリフェニレンスルフィド；ポリスルホン；ポリエーテルケトン等が挙げられる。
　また、前記樹脂としては、例えば、前記ポリエステルとそれ以外の樹脂との混合物等のポリマーアロイも挙げられる。前記ポリエステルとそれ以外の樹脂とのポリマーアロイは、ポリエステル以外の樹脂の量が比較的少量であるものが好ましい。
　また、前記樹脂としては、例えば、ここまでに例示した前記樹脂の１種又は２種以上が架橋した架橋樹脂；ここまでに例示した前記樹脂の１種又は２種以上を用いたアイオノマー等の変性樹脂も挙げられる。 The first substrate 11 is in the form of a sheet or a film, and examples of the constituent material thereof include various resins.
Examples of the resin include polyethylenes such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE); polyethylene other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene and norbornene resin Polyolefins; Ethylene copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer (ethylene as monomer Copolymers obtained by using a vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (resin obtained by using vinyl chloride as a monomer), polystyrene, polycycloolefin, polyethylene terephthalate, polyethylene Nafta Polyesters such as polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, wholly aromatic polyesters in which all constituent units have an aromatic cyclic group; Polymers; poly (meth) acrylic acid esters; polyurethanes; polyurethane acrylates; polyimides; polyamides; polycarbonates; fluorocarbons; polyacetals; modified polyphenylene oxides; polyphenylene sulfides; polysulfones;
Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and other resin, are also mentioned, for example. The polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
Further, as the resin, for example, a crosslinked resin obtained by crosslinking one or more of the above-described resins exemplified so far; modification of an ionomer using one or more of the above-described resins exemplified so far Resin is also mentioned.
　第１基材１１を構成する樹脂は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The resin constituting the first substrate 11 may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
　第１基材１１は１層（単層）のみでもよいし、２層以上の複数層でもよく、複数層である場合、これら複数層は、互いに同一でも異なっていてもよく、これら複数層の組み合わせは特に限定されない。 The first substrate 11 may be only one layer (single layer) or may be a plurality of layers of two or more layers, and in the case of a plurality of layers, the plurality of layers may be the same or different from each other. The combination is not particularly limited.
　第１基材１１の厚さは、２５～１５０μｍであることが好ましい。
　ここで、「第１基材１１の厚さ」とは、第１基材１１全体の厚さを意味し、例えば、複数層からなる第１基材１１の厚さとは、第１基材１１を構成するすべての層の合計の厚さを意味する。 The thickness of the first substrate 11 is preferably 25 to 150 μm.
Here, "the thickness of the first base material 11" means the thickness of the entire first base material 11, and for example, the thickness of the first base material 11 composed of a plurality of layers refers to the first base material 11 Means the total thickness of all the layers that make up.
　緩衝層１２は、緩衝層１２とこれに隣接する層へ加えられる力に対して、緩衝作用を有する。ここでは、「緩衝層と隣接する層」として、硬化性樹脂フィルム１３’を示している。 The buffer layer 12 has a buffering action on the force applied to the buffer layer 12 and the layer adjacent thereto. Here, as the “layer adjacent to the buffer layer”, the curable resin film 13 ′ is shown.
　緩衝層１２は、シート状又はフィルム状であり、エネルギー線硬化性であることが好ましい。エネルギー線硬化性である緩衝層１２は、エネルギー線硬化させることで、後述する硬化性樹脂フィルム１３’からの剥離がより容易となる。 The buffer layer 12 is in the form of a sheet or a film, and is preferably energy ray curable. The energy ray-curable buffer layer 12 can be more easily peeled off from a curable resin film 13 'described later by energy ray curing.
　緩衝層１２の構成材料としては、例えば、各種粘着性樹脂が挙げられる。緩衝層１２がエネルギー線硬化性である場合には、その構成材料としては、エネルギー線硬化に必要な各種成分も挙げられる。 As a constituent material of the buffer layer 12, various adhesive resins are mentioned, for example. When the buffer layer 12 is energy ray curable, the constituent materials thereof also include various components necessary for energy ray curing.
　緩衝層１２は１層（単層）のみでもよいし、２層以上の複数層でもよく、複数層である場合、これら複数層は、互いに同一でも異なっていてもよく、これら複数層の組み合わせは特に限定されない。 The buffer layer 12 may be only one layer (single layer) or may be a plurality of layers of two or more layers, and in the case of multiple layers, these multiple layers may be the same or different from one another, and the combination of these multiple layers is It is not particularly limited.
　緩衝層１２の厚さは、６０～６７５μｍであることが好ましい。
　ここで、「緩衝層１２の厚さ」とは、緩衝層１２全体の厚さを意味し、例えば、複数層からなる緩衝層１２の厚さとは、緩衝層１２を構成するすべての層の合計の厚さを意味する。 The thickness of the buffer layer 12 is preferably 60 to 675 μm.
Here, "the thickness of the buffer layer 12" means the entire thickness of the buffer layer 12, and, for example, the thickness of the buffer layer 12 composed of a plurality of layers is the total of all the layers constituting the buffer layer 12. Means the thickness of.
　貼付工程においては、熱硬化性樹脂フィルム１３’のうち、半導体ウエハ９’に対向している側の露出面（本明細書においては、「第１面」と称することがある）１３’ａを、半導体ウエハ９’のバンプ形成面９ａに圧着させることで、熱硬化性樹脂フィルム１３’を前記バンプ形成面９ａに貼付できる。 In the sticking step, the exposed surface (which may be referred to as a “first surface” in the present specification) 13′a of the thermosetting resin film 13 ′ on the side facing the semiconductor wafer 9 ′. The thermosetting resin film 13 'can be attached to the bump forming surface 9a by pressure bonding to the bump forming surface 9a of the semiconductor wafer 9'.
　貼付工程においては、硬化性樹脂フィルム１３’を加熱しながらバンプ形成面９ａに貼付することが好ましい。このようにすることで、硬化性樹脂フィルム１３’とバンプ形成面９ａとの間、並びに、硬化性樹脂フィルム１３’とバンプ９１の表面９１ａとの間、のいずれにおいても、空隙部の発生をより抑制できる。また最終的に、バンプの頭頂部において、第１保護膜残留物の残存を抑制する効果がより高くなる。 In the attaching step, it is preferable to attach the curable resin film 13 'to the bump forming surface 9a while heating. In this manner, the generation of the void is caused between the curable resin film 13 'and the bump forming surface 9a and between the curable resin film 13' and the surface 91a of the bump 91. It can suppress more. Finally, at the top of the bump, the effect of suppressing the remaining of the first protective film residue becomes higher.
　このときの硬化性樹脂フィルム１３’の加熱温度は、過度な高温でなければよく、例えば、６０～１００℃であることが好ましい。ここで、「過度な高温」とは、例えば、硬化性樹脂フィルム１３’が熱硬化性である場合には、硬化性樹脂フィルム１３’の熱硬化が進行するなど、硬化性樹脂フィルム１３’に目的外の作用が発現してしまう温度を意味する。 The heating temperature of the curable resin film 13 'at this time is not required to be an excessively high temperature, and is preferably, for example, 60 to 100.degree. Here, “excessive high temperature” means, for example, when the curable resin film 13 ′ is thermosetting, the thermosetting of the curable resin film 13 ′ proceeds, etc., to the curable resin film 13 ′. It means the temperature at which an unintended effect appears.
　貼付工程において、硬化性樹脂フィルム１３’をバンプ形成面９ａに貼付するときに、硬化性樹脂フィルム１３’に加える圧力（本明細書においては、「貼付圧力」と称することがある）は、０．３～１ＭＰａであることが好ましい。 In the sticking step, when the curable resin film 13 ′ is attached to the bump forming surface 9a, the pressure applied to the curable resin film 13 ′ (sometimes referred to as “sticking pressure” in the present specification) is 0. The pressure is preferably in the range of 3 to 1 MPa.
　貼付工程により、積層構造体（１）１０１を形成した後は、この積層構造体（１）１０１をそのまま次工程で用いてもよいが、必要に応じて、半導体ウエハ９’のバンプ形成面９ａとは反対側の面（裏面）９ｂを研削することにより、半導体ウエハ９’の厚さを調節してもよい。
　半導体ウエハ９’の裏面９ｂの研削は、グラインダーを用いる方法等の、公知の方法で行うことができる。 After the laminated structure (1) 101 is formed by the attaching step, the laminated structure (1) 101 may be used as it is in the next step, but if necessary, the bump forming surface 9a of the semiconductor wafer 9 ' The thickness of the semiconductor wafer 9 'may be adjusted by grinding the opposite surface (back surface) 9b.
Grinding of the back surface 9b of the semiconductor wafer 9 'can be performed by a known method such as a method using a grinder.
　半導体ウエハ９’の裏面９ｂを研削しない場合には、半導体ウエハ９’のバンプを除いた部位の厚さは、先に説明した、半導体チップのバンプを除いた部位の厚さと同じであることが好ましい。
　半導体ウエハ９’の裏面９ｂを研削する場合には、研削前における半導体ウエハ９’のバンプを除いた部位の厚さは、４００～１２００μｍであることが好ましく、６５０～７８０μｍであることがより好ましい。 When the back surface 9b of the semiconductor wafer 9 'is not ground, the thickness of the portion excluding the bumps of the semiconductor wafer 9' is the same as the thickness of the portion excluding the bumps of the semiconductor chip described above. preferable.
When grinding the back surface 9b of the semiconductor wafer 9 ', the thickness of the portion excluding the bumps of the semiconductor wafer 9' before grinding is preferably 400 to 1200 μm, and more preferably 650 to 780 μm. .
　貼付工程により、積層構造体（１）１０１を形成した後は、積層構造体（１）１０１中の熱硬化性樹脂フィルム１３’から、第１支持シート１０を剥離させる。半導体ウエハ９’の裏面９ｂを研削した場合には、この研削後に、第１支持シート１０を剥離させることが好ましい。
　このような工程を行うことで、図５（ｂ）に示すように、半導体ウエハ９’のバンプ形成面９ａに、熱硬化性樹脂フィルム１３’を備えて構成された、積層構造体（２）（すなわち、硬化性樹脂フィルム付き半導体ウエハ）１０２が得られる。
　積層構造体（２）１０２においては、半導体ウエハ９’のバンプ９１の頭頂部９１０は、硬化性樹脂フィルム１３’を貫通して、突出している。 After forming the laminated structure (1) 101 in the sticking step, the first support sheet 10 is peeled off from the thermosetting resin film 13 ′ in the laminated structure (1) 101. When the back surface 9 b of the semiconductor wafer 9 ′ is ground, it is preferable to peel off the first support sheet 10 after the grinding.
By performing such a process, as shown in FIG. 5B, a laminated structure (2) is provided, which is provided with a thermosetting resin film 13 'on the bump formation surface 9a of the semiconductor wafer 9'. That is, a semiconductor wafer with a curable resin film is obtained.
In the laminated structure (2) 102, the top portions 910 of the bumps 91 of the semiconductor wafer 9 'protrude through the curable resin film 13'.
　緩衝層１２がエネルギー線硬化性である場合には、エネルギー線の照射により、緩衝層１２を硬化させて、緩衝層１２の粘着性を低下させた後に、熱硬化性樹脂フィルム１３’から第１支持シート１０を剥離させることが好ましい。 When the buffer layer 12 is energy ray curable, the buffer layer 12 is cured by irradiation of energy rays to reduce the adhesiveness of the buffer layer 12, and then the first thermosetting resin film 13 ′ is removed from the thermosetting resin film 13 ′. It is preferable to peel off the support sheet 10.
＜第１保護膜形成工程＞
　前記製造方法においては、前記貼付工程後に前記第１保護膜形成工程を行い、図５（ｃ）に示すように、貼付後の硬化性樹脂フィルム１３’を硬化させることにより、第１保護膜１３を形成する。
　積層構造体（１）１０１を形成した場合には、第１保護膜形成工程は、上述の第１支持シート１０の剥離後に行うことができる。
　また、半導体ウエハ９’の裏面９ｂを研削した場合には、第１保護膜形成工程は、前記裏面９ｂの研削後に行うことができる。
　本工程を行うことにより、半導体ウエハ９’のバンプ形成面９ａに、第１保護膜１３を備えて構成された、積層構造体（３）（すなわち、第１保護膜付き半導体ウエハ）１０３が得られる。 <First Protective Film Forming Step>
In the manufacturing method, the first protective film forming step is performed after the sticking step, and as shown in FIG. 5C, the first protective film 13 is cured by curing the curable resin film 13 ′ after the sticking. Form
When forming laminated structure (1) 101, a 1st protective film formation process can be performed after peeling of the above-mentioned 1st support sheet 10. As shown in FIG.
When the back surface 9b of the semiconductor wafer 9 'is ground, the first protective film forming step can be performed after the grinding of the back surface 9b.
By performing this step, the laminated structure (3) (that is, the semiconductor wafer with a first protective film) 103 configured to include the first protective film 13 on the bump formation surface 9a of the semiconductor wafer 9 'is obtained. Be
　硬化性樹脂フィルム１３’の硬化条件は、第１保護膜が十分にその機能を発揮できる程度の硬化度となる限り特に限定されず、熱硬化性樹脂フィルムの種類に応じて、適宜選択すればよい。 The curing conditions of the curable resin film 13 ′ are not particularly limited as long as the first protective film has a curing degree sufficient to exhibit its function, and may be appropriately selected according to the type of the thermosetting resin film. Good.
　硬化性樹脂フィルム１３’が熱硬化性である場合には、硬化性樹脂フィルム１３’の熱硬化時において、加熱温度は１００～１８０℃であることが好ましく、加熱時間は０．５～５時間であることが好ましい。硬化性樹脂フィルム１３’の熱硬化時においては、硬化性樹脂フィルム１３’を加圧してもよく、その場合の加圧圧力は０．３～１ＭＰａであることが好ましい。 When the curable resin film 13 'is thermosetting, the heating temperature is preferably 100 to 180 ° C. and the heating time is 0.5 to 5 hours at the time of thermosetting of the curable resin film 13'. Is preferred. At the time of heat curing of the curable resin film 13 ′, the curable resin film 13 ′ may be pressurized, and in this case, the pressure is preferably 0.3 to 1 MPa.
　硬化性樹脂フィルム１３’がエネルギー線硬化性である場合には、硬化性樹脂フィルム１３’のエネルギー線硬化時において、エネルギー線の照度は１８０～２８０ｍＷ／ｃｍ２であることが好ましく、エネルギー線の光量は４５０～１５００ｍＪ／ｃｍ２であることが好ましい。 When the curable resin film 13 'is energy ray curable, the illuminance of the energy ray is preferably 180 to 280 mW / cm 2 at the time of energy ray curing of the curable resin film 13'. The light quantity is preferably 450 to 1500 mJ / cm 2 .
　図５（ｂ）に示す積層構造体（２）（硬化性樹脂フィルム付き半導体ウエハ）１０２において、半導体ウエハ９’のバンプ９１の頭頂部９１０に、硬化性樹脂フィルム１３’に由来する残留物（硬化性樹脂フィルム残留物）が残存していなければ、第１保護膜形成工程後に、前記頭頂部９１０に第１保護膜残留物も存在しない。また、前記頭頂部９１０での、硬化性樹脂フィルム１３’に由来する残留物（硬化性樹脂フィルム残留物）の量が少なければ、第１保護膜形成工程後に、前記頭頂部９１０での第１保護膜残留物の量も少なくなる。 In the laminated structure (2) (semiconductor wafer with a curable resin film) 102 shown in FIG. 5B, a residue derived from the curable resin film 13 ′ on the top portion 910 of the bump 91 of the semiconductor wafer 9 ′ If the curable resin film residue does not remain, there is no first protective film residue on the crown 910 after the first protective film forming step. In addition, if the amount of residue (curable resin film residue) derived from the curable resin film 13 ′ at the top of the head 910 is small, after the first protective film forming step, the first at the top of the head 910 will be described. The amount of protective film residue also decreases.
＜分割工程＞
　前記製造方法においては、前記第１保護膜形成工程後に前記分割工程を行い、図５（ｄ）に示すように、半導体ウエハ９’を分割することにより、半導体チップ９を得る。
　本工程により、目的物である第１保護膜付き半導体チップ１が得られる。 <Division process>
In the manufacturing method, the dividing step is performed after the step of forming the first protective film, and as shown in FIG. 5D, the semiconductor wafer 9 'is divided to obtain the semiconductor chip 9.
By this process, the semiconductor chip 1 with a first protective film, which is an object, is obtained.
　半導体ウエハ９’の分割は、公知の方法で行うことができる。
　例えば、ダイシングブレードを用いてダイシングすることにより、半導体ウエハ９’を分割する場合には、積層構造体（３）（第１保護膜付き半導体ウエハ）１０３中の、半導体ウエハ９’の裏面９ｂに、ダイシングシート（又はダイシングテープ）を貼付して、以降、公知の方法でダイシングできる。
　なお、本明細書においては、このように、半導体ウエハのバンプ形成面に第１保護膜を備え、半導体ウエハの裏面にダイシングシートを備えて構成されたものを、「積層構造体（５）」と称することがある。また、この積層構造体（５）中の半導体ウエハを第１保護膜とともに個片化し、半導体チップを形成したものを「積層構造体（６）」と称することがある。 The division of the semiconductor wafer 9 'can be performed by a known method.
For example, in the case where the semiconductor wafer 9 'is divided by dicing using a dicing blade, the back surface 9b of the semiconductor wafer 9' in the laminated structure (3) (semiconductor wafer with first protective film) 103 is used. , And a dicing sheet (or dicing tape) may be attached, and thereafter dicing may be performed by a known method.
In the present specification, as described above, a structure in which the first protective film is provided on the bump formation surface of the semiconductor wafer and the dicing sheet is provided on the back surface of the semiconductor wafer is referred to as “laminated structure (5)”. It may be called. In addition, the semiconductor wafer in this laminated structure (5) may be singulated together with the first protective film, and a semiconductor chip may be formed, which may be referred to as "laminated structure (6)".
　ダイシングシートとして、その貼付対象物（例えば、半導体チップ）に接触する層がエネルギー線硬化性であるものを用いた場合には、ダイシング後、エネルギー線の照射により、この層を硬化させて粘着性を低下させることにより、その貼付対象物からダイシングシートをより容易に取り除くことができる。 When the layer in contact with the object to be attached (for example, a semiconductor chip) is energy ray curable as the dicing sheet, this layer is cured by irradiation of energy rays after dicing and tackiness is obtained. The dicing sheet can be more easily removed from the object to be attached.
　半導体ウエハ９’をダイシングする場合には、上述のダイシングシートに代えて、第２保護膜形成用シートを用いてもよい。
　第２保護膜形成用シートは、半導体チップの裏面に上述の第２保護膜を形成するための保護膜形成用フィルムが、ダイシングシート上に形成された構成を有する。第２保護膜形成用シートを用いた場合には、ダイシング後にダイシングシートが取り除かれ、最終的には、前記裏面に第２保護膜が貼付された状態の半導体チップが得られる。すなわち、先に説明した、半導体チップの裏面に第２保護膜を備えた第１保護膜付き半導体チップは、このような製造方法により得られる。 When dicing the semiconductor wafer 9 ′, a second protective film-forming sheet may be used in place of the above-described dicing sheet.
The second protective film-forming sheet has a configuration in which a protective film-forming film for forming the above-mentioned second protective film on the back surface of the semiconductor chip is formed on the dicing sheet. When the second protective film-forming sheet is used, the dicing sheet is removed after dicing, and finally, a semiconductor chip in a state in which the second protective film is attached to the back surface is obtained. That is, the semiconductor chip with a first protective film provided with the second protective film on the back surface of the semiconductor chip described above can be obtained by such a manufacturing method.
　前記製造方法においては、第１保護膜形成工程直後の段階で、上述のように、バンプ９１の頭頂部９１０において、第１保護膜残留物の残存が抑制されている。したがって、目的物である第１保護膜付き半導体チップ１のバンプ９１の頭頂部９１０において、第１保護膜残留物の残存が抑制される。 In the manufacturing method, the residual of the first protective film residue is suppressed at the top portion 910 of the bump 91 as described above immediately after the step of forming the first protective film. Therefore, in the top portion 910 of the bump 91 of the semiconductor chip 1 with a first protective film, which is the object, the remaining of the first protective film residue is suppressed.
　このように、第１保護膜形成工程直後の段階で、バンプ９１の頭頂部９１０において、第１保護膜残留物の残存が抑制されるためには、先の説明のように、積層構造体（２）（硬化性樹脂フィルム付き半導体ウエハ）１０２の段階で、半導体ウエハ９’のバンプ９１の頭頂部９１０において、硬化性樹脂フィルム１３’に由来する残留物（硬化性樹脂フィルム残留物）の残存が抑制されていることが必要である。そのためには、例えば、硬化性樹脂フィルム１３’として、その残留物がバンプ９１の頭頂部９１０に残存し難いものを用いればよい。そして、前記貼付工程において、Ｓ（Ｃ）／Ｓ（Ｓｎ）値が０．３２以下となるように、バンプ９１の頭頂部９１０を硬化性樹脂フィルム１３’から突出させればよい。 As described above, in order to suppress the remaining of the first protective film residue at the top portion 910 of the bump 91 immediately after the first protective film formation step, as described above, the laminated structure ( 2) Residue (curable resin film residue) derived from the curable resin film 13 'at the top portion 910 of the bumps 91 of the semiconductor wafer 9' at the stage of (semiconductor wafer with curable resin film) 102 Needs to be suppressed. For that purpose, for example, as the curable resin film 13 ′, it is preferable to use one which hardly leaves the residue on the top portion 910 of the bump 91. Then, in the attaching process, the top portion 910 of the bump 91 may be protruded from the curable resin film 13 ′ such that the S (C) / S (Sn) value is 0.32 or less.
　このような本発明の効果を顕著に得易い硬化性樹脂フィルム１３’としては、先に説明したものが挙げられる。
　すなわち、熱硬化性樹脂フィルムの場合であれば、樹脂層形成用組成物（ＩＩＩ）として、重合体成分（Ａ）、エポキシ樹脂（Ｂ１）等の樹脂成分の重量平均分子量が小さい範囲のもの、充填材（Ｄ）の平均粒径が小さい範囲のもの、充填材（Ｄ）の含有量が少ない範囲のもの、等を用いることが好ましい。エポキシ樹脂（Ｂ１）としては、常温で液状のものを用いることが好ましい。 As curable resin film 13 'which is easy to acquire the effect of such this invention notably, what was demonstrated previously is mentioned.
That is, in the case of a thermosetting resin film, as the composition (III) for forming a resin layer, one having a small weight average molecular weight of a resin component such as a polymer component (A) or an epoxy resin (B1), It is preferable to use one having a range in which the average particle diameter of the filler (D) is small, one having a range in which the content of the filler (D) is small, and the like. As an epoxy resin (B1), it is preferable to use what is liquid at normal temperature.
　一方、積層構造体（２）（硬化性樹脂フィルム付き半導体ウエハ）１０２の段階で、半導体ウエハ９’のバンプ９１の頭頂部９１０において、硬化性樹脂フィルム１３’に由来する残留物（硬化性樹脂フィルム残留物）の残存が抑制されていない場合には、最終的に、第１保護膜付き半導体チップのバンプの頭頂部において、第１保護膜残留物が残存しないか、又はその量が少なくなるような工程を、別途行うことが必要である。このような工程が、前記残留物低減工程である。 On the other hand, at the stage of the laminated structure (2) (semiconductor wafer with curable resin film), a residue (curable resin) derived from the curable resin film 13 ′ at the top portion 910 of the bumps 91 of the semiconductor wafer 9 ′. In the case where the film residue is not suppressed, finally, the first protective film residue does not remain or is reduced at the top of the bump of the semiconductor chip with the first protective film. It is necessary to carry out such a process separately. Such a process is the residue reduction process.
＜残留物低減工程＞
　すなわち、前記残留物低減工程は、前記貼付工程の後に、前記Ｓ（Ｃ）／Ｓ（Ｓｎ）の値が０．３２以下となるように、バンプ９１上の残留物の量を低減する工程である。より具体的には、残留物低減工程は、前記貼付工程の後、目的とする第１保護膜付き半導体チップを得るまでの、いずれかの段階で行う。そして、残留物低減工程においては、例えば、半導体ウエハ９’若しくは半導体チップ９のバンプ９１の頭頂部９１０に残存している、硬化性樹脂フィルム残留物又は第１保護膜残留物等の、残留物の量を低減する。ここで、「残留物の量を低減する」とは、残留物が存在しないか、又は残留物が存在しても、その影響が認められない程度に残留物の量が少ない状態とすることを意味する。 <Residue reduction process>
That is, the residue reduction step is a step of reducing the amount of residue on the bumps 91 so that the value of the S (C) / S (Sn) becomes 0.32 or less after the attachment step. is there. More specifically, the residue reduction step is performed at any stage after the attaching step until the target semiconductor chip with a protective film is obtained. Then, in the residue reduction step, for example, a residue such as a curable resin film residue or a first protective film residue remaining on the top portion 910 of the bump 91 of the semiconductor wafer 9 ′ or the semiconductor chip 9. Reduce the amount of Here, "to reduce the amount of residue" means that the amount of residue is small to such an extent that the effect is not recognized even if the residue is not present or is present. means.
　前記製造方法の一実施形態においては、前記第１保護膜形成工程の後に、残留物低減工程を行い、バンプ９１上の第１保護膜残留物の量を低減する。
　図７は、本実施形態における残留物低減工程の一例を、模式的に説明するための拡大断面図である。 In one embodiment of the manufacturing method, a residue reducing step is performed after the first protective film forming step to reduce the amount of the first protective film residue on the bumps 91.
FIG. 7 is an enlarged cross-sectional view for schematically explaining an example of the residue reduction step in the present embodiment.
　本実施形態においては、第１保護膜形成工程終了後に、先に説明した積層構造体（３）（第１保護膜付き半導体ウエハ）１０３中のバンプ９１の頭頂部９１０に、第１保護膜残留物１３１が残存していることがある。図７（ａ）は、このような積層構造体（３）を示しており、この積層構造体（３）１０３は、図５中の積層構造体（３）１０３とは、第１保護膜残留物１３１の残存量が多い点で異なっている。 In the present embodiment, after completion of the first protective film forming step, the first protective film remains on the top portion 910 of the bumps 91 in the laminated structure (3) (semiconductor wafer with first protective film) 103 described above. The object 131 may remain. FIG. 7 (a) shows such a laminated structure (3), and the laminated structure (3) 103 is the same as the laminated structure (3) 103 in FIG. The difference is that the remaining amount of the object 131 is large.
　本実施形態の残留物低減工程では、積層構造体（３）１０３中の、半導体ウエハ９’のバンプ９１の上部に対して、プラズマを照射することにより、バンプ９１の上部の第１保護膜残留物１３１の量を低減する。これにより、図７（ｂ）に示すように、図５（ｃ）で示したものと同様に、バンプ９１の頭頂部９１０において、第１保護膜残留物１３１の残存が抑制されている積層構造体が得られる。本明細書においては、このように積層構造体（３）に対して残留物低減工程を行って得られたものを積層構造体（４）と称することがある。図７においては、符号１０４を付して、積層構造体（４）を示している。 In the residue reduction step of the present embodiment, the upper portion of the bump 91 of the semiconductor wafer 9 ′ in the laminated structure (3) 103 is irradiated with plasma to leave the first protective film remaining on the upper portion of the bump 91. Reduce the amount of objects 131. As a result, as shown in FIG. 7B, a laminated structure in which the remaining of the first protective film residue 131 is suppressed in the top portion 910 of the bumps 91 as in the case shown in FIG. 5C. Get the body. In the present specification, a product obtained by performing the residue reduction step on the laminated structure (3) in this manner may be referred to as a laminated structure (4). In FIG. 7, reference numeral 104 is given to indicate the laminated structure (4).
　残留物低減工程でのプラズマの照射条件は、第１保護膜残留物１３１の量を十分に低減できる限り、特に限定されない。
　例えば、テトラフルオロメタン（ＣＦ４）ガス、酸素ガス等の反応性ガスの存在下、ガスの圧力を８０～１２０Ｐａとし、加える電力を２００～３００Ｗとして、プラズマを０．５～５分照射すればよい。ただし、この条件は、プラズマの照射条件の一例である。 The irradiation conditions of the plasma in the residue reduction step are not particularly limited as long as the amount of the first protective film residue 131 can be sufficiently reduced.
For example, if the pressure of the gas is 80 to 120 Pa, the applied power is 200 to 300 W, and the plasma is irradiated for 0.5 to 5 minutes in the presence of a reactive gas such as tetrafluoromethane (CF 4 ) gas or oxygen gas. Good. However, this condition is an example of the plasma irradiation condition.
　残留物低減工程でのプラズマの照射範囲は、第１保護膜残留物１３１の量を十分に低減できる限り、特に限定されず、少なくともバンプ９１の上部が含まれていればよい。そして、残留物低減工程においては、例えば、第１保護膜１３を備えた半導体ウエハ９’の、バンプ９１を有する側の全面に、プラズマを照射してもよい。 The irradiation range of plasma in the residue reduction step is not particularly limited as long as the amount of the first protective film residue 131 can be sufficiently reduced, and at least the upper portion of the bump 91 may be included. Then, in the residue reduction step, for example, plasma may be irradiated on the entire surface of the semiconductor wafer 9 ′ provided with the first protective film 13 on the side having the bumps 91.
　ここでは、第１保護膜形成工程の後で、かつ分割工程の前に、残留物低減工程を行う場合について説明したが、本実施形態での残留物低減工程は、分割工程の後に行ってもよい。この場合のプラズマの照射対象物は、半導体ウエハ９’ではなく半導体チップ９となる（換言すると、積層構造体（３）１０３ではなく、第１保護膜残留物１３１が残存する第１保護膜付き半導体チップ１となる）。この点以外は、上述の場合と同じ方法で、残留物低減工程を行うことができる。 Here, the case where the residue reduction step is performed after the first protective film formation step and before the division step has been described, but the residue reduction step in the present embodiment may be performed after the division step. Good. The object to be irradiated with plasma in this case is not the semiconductor wafer 9 'but the semiconductor chip 9 (in other words, with the first protective film in which the first protective film residue 131 remains, not the laminated structure (3) 103) It becomes a semiconductor chip 1). A residue reduction process can be performed by the same method as the above-mentioned case except this point.
　また、ここでは、プラズマの照射により、第１保護膜残留物１３１の量を低減する場合について説明したが、第１保護膜残留物１３１の量を低減する方法としては、これ以外に、例えば、第１保護膜残留物１３１に微粒子を衝突させる方法が挙げられる。
　この場合、前記微粒子は、少なくともバンプ９１の上部に対して衝突させればよく、微粒子を衝突させる範囲は、上述のプラズマの照射範囲と同様とすることができる。 Furthermore, although the case of reducing the amount of the first protective film residue 131 by plasma irradiation has been described here, as another method for reducing the amount of the first protective film residue 131, for example, The method of making microparticles collide with the 1st protective film residue 131 is mentioned.
In this case, the fine particles may collide with at least the upper portion of the bumps 91, and the range in which the fine particles collide can be made similar to the above-described irradiation range of plasma.
　前記微粒子は、第１保護膜残留物１３１の量を低減可能であれば、特に限定されず、その具体例としては、ケイ砂、アルミナ、ガラス等の無機材料からなる研磨材；ドライアイス微粒子等が挙げられる。
　これらの中でも、気化によって、第１保護膜付き半導体チップでの前記微粒子の残存を顕著に容易に抑制できる点では、前記微粒子はドライアイス微粒子であることが好ましい。 The fine particles are not particularly limited as long as the amount of the first protective film residue 131 can be reduced, and specific examples thereof include abrasives made of an inorganic material such as silica sand, alumina, glass, etc .; dry ice fine particles etc. Can be mentioned.
Among these, it is preferable that the fine particles are dry ice fine particles in that the remaining of the fine particles in the semiconductor chip with the first protective film can be remarkably easily suppressed by the vaporization.
　前記製造方法の他の実施形態においては、前記貼付工程の後に、残留物低減工程を行い、バンプ９１上の硬化性樹脂フィルム残留物の量を低減する。
　図８は、本実施形態における残留物低減工程の他の例を、模式的に説明するための拡大断面図である。 In another embodiment of the manufacturing method, a residue reducing step is performed after the attaching step to reduce the amount of the curable resin film residue on the bumps 91.
FIG. 8 is an enlarged cross-sectional view for schematically illustrating another example of the residue reduction step in the present embodiment.
　本実施形態においては、貼付工程終了後に、先に説明した積層構造体（２）（硬化性樹脂フィルム付き半導体ウエハ）１０２中のバンプ９１の頭頂部９１０に、硬化性樹脂フィルム残留物１３１’が残存していることがある。図８（ａ）は、このような積層構造体（２）を示しており、この積層構造体（２）１０２は、図５中の積層構造体（２）１０２とは、硬化性樹脂フィルム残留物１３１’の残存量が多い点で異なっている。 In the present embodiment, after completion of the attaching process, the curable resin film residue 131 ′ is present on the top portion 910 of the bumps 91 in the laminated structure (2) (semiconductor wafer with curable resin film) 102 described above. It may remain. FIG. 8 (a) shows such a laminated structure (2), and the laminated structure (2) 102 is the same as the laminated structure (2) 102 in FIG. The difference is that the remaining amount of the object 131 ′ is large.
　本実施形態の残留物低減工程では、積層構造体（２）１０２中の、半導体ウエハ９’の少なくともバンプ９１の上部に対して、プラズマを照射することにより、バンプ９１の上部の硬化性樹脂フィルム残留物１３１’の量を低減する。これにより、図８（ｂ）に示すように、図５（ｂ）で示したものと同様に、バンプ９１の頭頂部９１０において、硬化性樹脂フィルム残留物１３１’の残存が抑制されている積層構造体が得られる。本明細書においては、このように積層構造体（２）に対して残留物低減工程を行って得られたものを積層構造体（１０）と称することがある。図８においては、符号１１０を付して、積層構造体（１０）を示している。 In the residue reduction step of the present embodiment, the upper portion of at least the bumps 91 of the semiconductor wafer 9 ′ in the laminated structure (2) 102 is irradiated with plasma to form a curable resin film on the upper portions of the bumps 91. Reduce the amount of residue 131 '. Thereby, as shown in FIG. 8 (b), in the same manner as shown in FIG. 5 (b), in the top portion 910 of the bump 91, the lamination in which the remaining of the curable resin film residue 131 'is suppressed. A structure is obtained. In the present specification, a product obtained by performing the residue reduction step on the laminated structure (2) in this manner may be referred to as a laminated structure (10). In FIG. 8, reference numeral 110 is attached to indicate the laminated structure (10).
　本実施形態におけるプラズマの照射条件は、照射対象物が異なる点以外は、先に説明した照射条件と同様とすることができる。 The irradiation conditions of plasma in the present embodiment can be the same as the irradiation conditions described above except that the irradiation object is different.
　また、本実施形態においても、先に説明した場合と同様に、プラズマの照射に代えて、硬化性樹脂フィルム残留物１３１’に微粒子を衝突させる方法を採用することによって、硬化性樹脂フィルム残留物１３１’の量を低減できる。本実施形態においても、先に説明した場合と同様の方法で、微粒子を衝突させることができる。 Also in the present embodiment, as in the case described above, a method of causing fine particles to collide with the curable resin film residue 131 ′ instead of plasma irradiation is used, thereby the curable resin film residue is The amount of 131 'can be reduced. Also in this embodiment, the fine particles can be made to collide in the same manner as described above.
　ここまでは、残留物低減工程において、バンプ９１上の残留物の量だけを低減する方法を採用したものについて説明したが、残留物低減工程においては、バンプ９１上の残留物を、そのバンプ９１の付着部位とともに除去する方法を採用してもよい。 So far, in the residue reduction step, the method for reducing only the amount of residue on the bumps 91 has been described, but in the residue reduction step, the residue on the bumps 91 is the bump 91 A method of removing along with the attachment site of
　すなわち、前記製造方法のさらに他の実施形態においては、前記第１保護膜形成工程の後に、残留物低減工程を行うことにより、バンプ９１上の第１保護膜残留物を、そのバンプ９１の付着部位とともに除去する。
　図９は、本実施形態における残留物低減工程のさらに他の例を、模式的に説明するための拡大断面図である。 That is, in still another embodiment of the manufacturing method, by performing the residue reducing step after the first protective film forming step, the first protective film residue on the bumps 91 is attached to the bumps 91. Remove along with the site.
FIG. 9 is an enlarged cross-sectional view for schematically illustrating still another example of the residue reduction step in the present embodiment.
　先に説明したとおり、本実施形態においては、第１保護膜形成工程終了後に、先に説明した積層構造体（３）（第１保護膜付き半導体ウエハ）１０３中のバンプ９１の頭頂部９１０に、第１保護膜残留物１３１が残存していることがある。図９（ａ）は、このような積層構造体（３）を示しており、この積層構造体（３）１０３は、図５中の積層構造体（３）１０３とは、第１保護膜残留物１３１の残存量が多い点で異なっている。 As described above, in the present embodiment, after the completion of the first protective film forming step, on the top portions 910 of the bumps 91 in the laminated structure (3) (semiconductor wafer with first protective film) 103 described above. The first protective film residue 131 may remain. FIG. 9 (a) shows such a laminated structure (3), and the laminated structure (3) 103 is the same as the laminated structure (3) 103 in FIG. The difference is that the remaining amount of the object 131 is large.
　本実施形態の残留物低減工程では、積層構造体（３）１０３中の、半導体ウエハ９’のバンプ９１の上部のうち、第１保護膜残留物１３１が残存している部位を、この第１保護膜残留物１３１ごと除去する。より具体的には、積層構造体（３）１０３において、半導体ウエハ９’のバンプ９１をその頂点から特定の距離だけ下の部位において切断し、切断片を除去することにより、バンプ９１の第１保護膜残留物１３１が残存している上部を、この第１保護膜残留物１３１ごと除去する。これにより、図９（ｂ）に示すように、バンプの形状が変化した積層構造体（１１）１１１が得られる。そして、積層構造体（３）１０３に代えて、この積層構造体（１１）１１１を用いることにより、最終的には、図３で示したものと同じ第１保護膜付き半導体チップ、すなわち、バンプ９２の頭頂部９２０において、第１保護膜残留物１３１の残存が抑制されている第１保護膜付き半導体チップ３が得られる。 In the residue reduction step of the present embodiment, the portion of the upper portion of the bump 91 of the semiconductor wafer 9 ′ in the laminated structure (3) 103 where the first protective film residue 131 remains is the first portion. The protective film residue 131 is removed together. More specifically, in the laminated structure (3) 103, the bump 91 of the semiconductor wafer 9 'is cut at a specific distance below the vertex thereof, and the cut piece is removed to thereby form the first bump 91. The upper part where the protective film residue 131 remains is removed together with the first protective film residue 131. Thereby, as shown in FIG.9 (b), laminated-structure (11) 111 which the shape of bump changed is obtained. Then, by using this laminated structure (11) 111 instead of the laminated structure (3) 103, finally, the same semiconductor chip with the first protective film as shown in FIG. 3, that is, the bumps The semiconductor chip 3 with the first protective film in which the remaining of the first protective film residue 131 is suppressed at the top of the head 92 of the 92 is obtained.
　上述のように、バンプ９１の特定部位を切断する方法としては、ダイシングブレードを用いてバンプ９１を切断する方法が挙げられる。
　この場合、積層構造体（３）１０３中の、半導体ウエハ９’の裏面９ｂに、ダイシングシートを貼付してから、バンプ９１の特定部位を切断することが好ましい。この場合のダイシングシートとしては、通常のダイシングシートを用いることができる。 As described above, as a method of cutting a specific portion of the bump 91, there is a method of cutting the bump 91 using a dicing blade.
In this case, it is preferable to cut a specific portion of the bump 91 after attaching a dicing sheet to the back surface 9 b of the semiconductor wafer 9 ′ in the laminated structure (3) 103. An ordinary dicing sheet can be used as the dicing sheet in this case.
　ダイシングブレードを用いたバンプ９１の特定部位の切断は、切断箇所が異なる点以外は、通常の半導体ウエハのダイシングの場合と同じ方法で行うことができる。
　例えば、ブレードの回転数は、２００００～４５０００ｒｐｍであることが好ましく、ブレードの送り速度（移動速度）は、1０～１００ｍｍ／ｓであることが好ましい。 The cutting of the specific portion of the bump 91 using a dicing blade can be performed by the same method as dicing of a normal semiconductor wafer except that the cutting portion is different.
For example, the rotation speed of the blade is preferably 20000 to 45000 rpm, and the feed speed (moving speed) of the blade is preferably 10 to 100 mm / s.
　なお、本明細書においては、このうようにバンプ９１の特定部位を切断する前の、積層構造体（３）中において、半導体ウエハのバンプ形成面に第１保護膜を備え、半導体ウエハの裏面にダイシングテープを備えて構成されたものを、「積層構造体（７）」と称することがある。 In the present specification, the first protective film is provided on the bump formation surface of the semiconductor wafer in the laminated structure (3) before the specific portion of the bump 91 is cut like this, and the back surface of the semiconductor wafer What is constituted by providing a dicing tape is sometimes referred to as "laminated structure (7)".
　残留物低減工程でのバンプ９１の切断部位は、第１保護膜残留物１３１の量を十分に低減できる限り、特に限定されない。
　例えば、半導体ウエハのバンプ形成面に対して平行な方向において、高さがＨであるバンプを切断する場合には、バンプの頂点から、好ましくは０．１５Ｈ～０．４Ｈのいずれかの距離だけ下の部位、より好ましくは０．１８Ｈ～０．３５Ｈのいずれかの距離だけ下の部位、さらに好ましくは０．２１Ｈ～０．３Ｈのいずれかの距離だけ下の部位が、バンプの切断部位である。
　例えば、半導体ウエハのバンプ形成面に対して平行ではない方向において、高さがＨであるバンプを切断する場合には、上述の数値範囲で特定される部位が切断部位に含まれるようにすることが好ましい。 The cut site of the bump 91 in the residue reduction step is not particularly limited as long as the amount of the first protective film residue 131 can be sufficiently reduced.
For example, in the case of cutting a bump whose height is H in a direction parallel to the bump formation surface of a semiconductor wafer, the distance from the vertex of the bump is preferably any distance of 0.15 H to 0.4 H The lower site, more preferably, the lower site by any distance of 0.18 H to 0.35 H, and further preferably, the lower site by any distance of 0.21 H to 0.3 H, is the cut site of the bump. is there.
For example, when cutting a bump whose height is H in a direction that is not parallel to the bump formation surface of the semiconductor wafer, the portion specified in the above numerical range should be included in the cut portion. Is preferred.
　本実施形態においては、積層構造体（３）１０３に代えて、この積層構造体（７）を用いて、以下、同様の工程を行うことにより、第１保護膜付き半導体チップ３が得られる。
　本実施形態においては、積層構造体（７）において、上記のようにバンプの特定部位が切断されたものを「積層構造体（８）」と称し、さらに、この積層構造体（８）中の半導体ウエハが第１保護膜とともに個片化されて、半導体チップとなったものを「積層構造体（９）」と称することがある。 In the present embodiment, the semiconductor chip 3 with the first protective film is obtained by performing the same process using the stacked structure (7) instead of the stacked structure (3) 103.
In the present embodiment, in the laminated structure (7), the one in which the specific part of the bump is cut as described above is referred to as "laminated structure (8)", and further, in the laminated structure (8). The semiconductor wafer may be singulated with the first protective film to form a semiconductor chip, which may be referred to as a “laminated structure (9)”.
　なお、本実施形態においては、バンプ９１の上部を第１保護膜残留物１３１ごと除去するが、目的とする第１保護膜付き半導体チップを得るまでのいずれかの段階における条件によっては、少量の第１保護膜残留物１３１がバンプ９２の頭頂部９２０に残存することがある。このような状態の第１保護膜付き半導体チップが、図４に示す第１保護膜付き半導体チップ４である。 In the present embodiment, the upper portion of the bump 91 is removed together with the first protective film residue 131, but depending on the conditions in any of the steps until the target semiconductor chip with the first protective film is obtained, a small amount of The first protective film residue 131 may remain on the top portion 920 of the bump 92. The semiconductor chip with a first protective film in such a state is the semiconductor chip 4 with a first protective film shown in FIG.
　ここでは、第１保護膜形成工程の後で、かつ分割工程の前に、残留物低減工程を行う場合について説明したが、本実施形態での残留物低減工程は、先に説明したように、分割工程の後に行ってもよい。この場合の切断対象物は、半導体ウエハ９’のバンプ９１ではなく半導体チップ９のバンプ９１となる（換言すると、積層構造体（３）ではなく、第１保護膜残留物１３１が残存する第１保護膜付き半導体チップ１となる）。この点以外は、上述の場合と同じ方法で、残留物低減工程を行うことができる。
　ただし、バンプ９１の特定部位の切断がより容易である点では、本実施形態での残留物低減工程は、第１保護膜形成工程の後で、かつ分割工程の前に行うことが好ましい。 Although the case of performing the residue reduction step after the first protective film formation step and before the division step has been described here, the residue reduction step in the present embodiment is as described above, It may be performed after the dividing step. The object to be cut in this case is not the bumps 91 of the semiconductor wafer 9 'but the bumps 91 of the semiconductor chip 9 (in other words, the first protective film residue 131 remains, not the laminated structure (3)). It becomes the semiconductor chip 1 with a protective film). A residue reduction process can be performed by the same method as the above-mentioned case except this point.
However, it is preferable to perform the residue reduction step in the present embodiment after the first protective film formation step and before the division step in that cutting of the specific portion of the bump 91 is easier.
　前記製造方法のさらに他の実施形態においては、前記貼付工程の後に、残留物低減工程を行い、バンプ９１上の硬化性樹脂フィルム残留物を、そのバンプ９１の付着部位とともに除去する。
　図１０は、本実施形態における残留物低減工程のさらに他の例を、模式的に説明するための拡大断面図である。 In still another embodiment of the manufacturing method, a residue reduction step is performed after the attaching step, and the curable resin film residue on the bump 91 is removed together with the attachment site of the bump 91.
FIG. 10 is an enlarged cross-sectional view for schematically illustrating still another example of the residue reduction step in the present embodiment.
　先に説明したとおり、本実施形態においては、貼付工程終了後に、先に説明した積層構造体（２）（硬化性樹脂フィルム付き半導体ウエハ）１０２中のバンプ９１の頭頂部９１０に、硬化性樹脂フィルム残留物１３１’が残存していることがある。図１０（ａ）は、このような積層構造体（２）を示しており、この積層構造体（２）１０２は、図５中の積層構造体（２）１０２とは、硬化性樹脂フィルム残留物１３１’の残存量が多い点で異なっている。 As described above, in the present embodiment, after completion of the attaching process, the curable resin is applied to the top portion 910 of the bumps 91 in the laminated structure (2) (semiconductor wafer with curable resin film) 102 described above. Film residue 131 'may remain. FIG. 10 (a) shows such a laminated structure (2), and the laminated structure (2) 102 is the same as the laminated structure (2) 102 in FIG. The difference is that the remaining amount of the object 131 ′ is large.
　本実施形態の残留物低減工程では、積層構造体（２）１０２中の、半導体ウエハ９’のバンプ９１の上部のうち、硬化性樹脂フィルム残留物１３１’が残存している部位を、この硬化性樹脂フィルム残留物１３１’ごと除去する。より具体的には、積層構造体（２）１０２において、半導体ウエハ９’のバンプ９１をその頂点から特定の距離だけ下の部位において切断し、切断片を除去することにより、バンプ９１の硬化性樹脂フィルム残留物１３１’が残存している上部を、この硬化性樹脂フィルム残留物１３１’ごと除去する。これにより、図１０（ｂ）に示すように、バンプの形状が変化した積層構造体（１２）１１２が得られる。そして、積層構造体（３）１０３に代えて、この積層構造体（１２）１１２を用いることにより、最終的には、図３で示したものと同じ第１保護膜付き半導体チップ、すなわち、バンプ９２の頭頂部９２０において、第１保護膜残留物１３１の残存が抑制されている第１保護膜付き半導体チップ３が得られる。 In the residue reduction step of the present embodiment, the portion of the upper portion of the bumps 91 of the semiconductor wafer 9 ′ in the laminated structure (2) 102 where the curable resin film residue 131 ′ remains is cured. Resin film residue 131 'together. More specifically, in the laminated structure (2) 102, the bumps 91 of the semiconductor wafer 9 'are cut at a specific distance below the apex thereof, and the cut pieces are removed, whereby the curability of the bumps 91 is achieved. The upper portion where the resin film residue 131 'remains is removed together with the curable resin film residue 131'. Thereby, as shown in FIG.10 (b), laminated-structure (12) 112 which the shape of bump changed is obtained. Then, by using this laminated structure (12) 112 instead of the laminated structure (3) 103, finally, the same semiconductor chip with the first protective film as shown in FIG. 3, that is, the bumps The semiconductor chip 3 with the first protective film in which the remaining of the first protective film residue 131 is suppressed at the top of the head 92 of the 92 is obtained.
　本実施形態におけるバンプ９１の切断条件は、切断対象物が異なる点以外は、先に説明した切断条件と同様とすることができる。 The cutting conditions of the bumps 91 in the present embodiment can be the same as the cutting conditions described above, except that the object to be cut is different.
　以上のように、ここまでは、図１及び図２に示すような、バンプの頭頂部が曲面である第１保護膜付き半導体チップの製造方法と、図３及び図４に示すような、バンプの頭頂部が平面である第１保護膜付き半導体チップの製造方法と、について説明した。
　これらのうち、バンプの頭頂部が平面である第１保護膜付き半導体チップの製造方法は、上述のとおり、半導体ウエハ又は半導体チップのバンプの一部を、これに付着している残留物とともに除去する工程（残留物低減工程）を有する。すなわち、このような残留物低減工程を有しない第１保護膜付き半導体チップの製造方法は、バンプの一部と、第１保護膜の形成に用いた材料の一部と、を無駄にすることがないという点で、残留物低減工程を有する第１保護膜付き半導体チップの製造方法よりも有利である。
　ただし、残留物低減工程を有する第１保護膜付き半導体チップの製造方法は、バンプの除去量を、目的を達成するための必要最低限の量とすることができ、過剰量となることを抑制できるという利点を有する。 As described above, the manufacturing method of the semiconductor chip with the first protective film, in which the top of the bump is a curved surface as shown in FIGS. 1 and 2, and the bumps as shown in FIGS. 3 and 4. The manufacturing method of the semiconductor chip with a 1st protective film whose top of the head is a plane was explained.
Among them, as described above, the method of manufacturing the semiconductor chip with a first protective film, in which the top of the bump is flat, removes a part of the bump of the semiconductor wafer or the semiconductor chip together with the residue adhering thereto. Process (residue reduction process). That is, the method of manufacturing a semiconductor chip with a first protective film without such a residue reduction process wastes a part of the bump and a part of the material used to form the first protective film. Is advantageous over the method of manufacturing a semiconductor chip with a first protective film having a residue reduction step in that
However, in the method of manufacturing the semiconductor chip with a first protective film having a residue reduction step, the amount of removal of the bumps can be made the minimum necessary amount to achieve the purpose, and the excessive amount is suppressed It has the advantage of being able to
　また、残留物低減工程を有しない製造方法で得られた第１保護膜付き半導体チップは、バンプの高さを高くし易いという点で、残留物低減工程を有する製造方法で得られた第１保護膜付き半導体チップよりも有利である。 In addition, the semiconductor chip with a first protective film obtained by the manufacturing method not having the residue reduction step can be obtained by the first manufacturing method having the residue reduction step in that the height of the bumps can be easily increased. It is advantageous over a semiconductor chip with a protective film.
　また、製造時に残留物低減工程を行う必要がある第１保護膜付き半導体チップにおいては、バンプのうち、半導体チップのバンプ形成面の近傍部位の面と、第１保護膜と、の間に、微細な空隙部が生じ易い傾向がある。これは、前記貼付工程において、バンプの頭頂部に硬化性樹脂フィルム残留物が残存し易い場合には、バンプの前記バンプ形成面の近傍部位の面と、硬化性樹脂フィルムと、の間に、微細な空隙部が生じ易い傾向があるためである。これに対して、残留物低減工程を有しない製造方法で得られた第１保護膜付き半導体チップは、前記空隙部が生じ難く、第１保護膜による保護効果がより高いという点で有利である。 Further, in the semiconductor chip with a first protective film which needs to carry out a residue reduction step at the time of manufacture, between the bump and the surface of a portion near the bump forming surface of the semiconductor chip and the first protective film, There is a tendency for fine gaps to easily occur. This is because, in the pasting process, when the residue of the curable resin film is likely to remain on the top of the bump, between the surface of the bump near the surface on which the bump is formed and the curable resin film, This is because a fine gap tends to be generated. On the other hand, the semiconductor chip with the first protective film obtained by the manufacturing method not having the residue reduction step is advantageous in that the void portion is not easily generated and the protective effect by the first protective film is higher. .
　ここまでは、おもに図１～図４に示す第１保護膜付き半導体チップの製造方法について説明したが、他の第１保護膜付き半導体チップも、その構造に基づいて必要とされる他の工程を、上述の製造方法において、適宜、適したタイミングで別途有する製造方法により、製造できる。 So far, the manufacturing method of the semiconductor chip with a first protective film shown in FIGS. 1 to 4 has been mainly described, but other semiconductor chips with a first protective film are also required other processes based on their structures. In the above-mentioned manufacturing method, it can manufacture suitably by the manufacturing method which has separately at suitable timing.
◇半導体チップ・第１保護膜積層体の評価方法
　本発明の半導体チップ・第１保護膜積層体の評価方法は、半導体チップと、前記半導体チップのバンプを有する面（バンプ形成面）に形成された第１保護膜と、を備えた、半導体チップ・第１保護膜積層体の評価方法であって、前記半導体チップ・第１保護膜積層体中の前記バンプの頭頂部について、エネルギー分散型Ｘ線分光法（ＥＤＸ）によって分析を行い、炭素の検出シグナルの強度Ｓ（Ｃ）と、スズの検出シグナルの強度Ｓ（Ｓｎ）と、を測定し、Ｓ（Ｃ）／Ｓ（Ｓｎ）の値が０．３２以下である場合には、前記半導体チップ・第１保護膜積層体を、目的とする第１保護膜付き半導体チップであると判定し、Ｓ（Ｃ）／Ｓ（Ｓｎ）の値が０．３２よりも大きい場合には、前記半導体チップ・第１保護膜積層体を、目的とする第１保護膜付き半導体チップではないと判定する。 評 価 Evaluation Method of Semiconductor Chip and First Protective Film Laminate The evaluation method of the semiconductor chip and first protective film laminate of the present invention is formed on the semiconductor chip and the surface (bump formation surface) of the semiconductor chip having bumps. An evaluation method of a semiconductor chip and a first protective film stack, comprising: a first protective film, wherein an energy dispersive type X is applied to a top of the bump in the semiconductor chip and the first protective film stack. Analysis is performed by line spectroscopy (EDX) to measure the intensity S (C) of the carbon detection signal and the intensity S (Sn) of the detection signal of tin, and the value of S (C) / S (Sn) When it is 0.32 or less, the semiconductor chip / first protective film laminate is determined to be a target semiconductor chip with a first protective film, and the value of S (C) / S (Sn) Is larger than 0.32, the semiconductor chip It is determined that the semiconductor chip / first protective film laminate is not a target semiconductor chip with a first protective film.
　すなわち、前記半導体チップ・第１保護膜積層体は、Ｓ（Ｃ）／Ｓ（Ｓｎ）値が特定されていない点以外は、上述の第１保護膜付き半導体チップと同じであり、Ｓ（Ｃ）／Ｓ（Ｓｎ）値の特定結果によって、第１保護膜付き半導体チップにもなり得るし、それ以外にもなり得る。 That is, the semiconductor chip / first protective film laminate is the same as the above-described semiconductor chip with a first protective film except that the S (C) / S (Sn) value is not specified, and S (C (C) Depending on the result of specifying the / S (Sn) value, the semiconductor chip with the first protective film may be or may be other than that.
　本発明の半導体チップ・第１保護膜積層体の評価方法によれば、評価対象である半導体チップ・第１保護膜積層体が、上述の本発明の第１保護膜付き半導体チップであるか否かを判定できる。そして、この半導体チップ・第１保護膜積層体が、そのバンプと基板との間の接合強度を高くできるものであるか否か、さらに、その半導体チップと基板との接合体における電気的接続度（導電性）を高くできるものであるか否か、について、判定できる。 According to the method for evaluating a semiconductor chip / first protective film laminate of the present invention, whether the semiconductor chip / first protective film laminate to be evaluated is the semiconductor chip with the first protective film of the present invention described above It can be determined. Then, whether or not the semiconductor chip / first protective film laminate can increase the bonding strength between the bumps and the substrate, and the degree of electrical connection in the joined body of the semiconductor chip and the substrate It can be determined whether (conductivity) can be increased.
　前記評価方法において、半導体チップ・第１保護膜積層体中のバンプの頭頂部についてのＥＤＸ分析は、先に説明した、第１保護膜付き半導体チップ中のバンプの頭頂部についてのＥＤＸ分析の場合と、同じ方法で行うことができる。 In the above evaluation method, the EDX analysis of the top of the bump in the semiconductor chip / first protective film laminate is the case of the EDX analysis of the top of the bump in the semiconductor chip with the first protective film described above. And can be done in the same way.
　第１保護膜付き半導体チップであると判定される程度にＳ（Ｃ）／Ｓ（Ｓｎ）値が小さい、判定前の半導体チップ・第１保護膜積層体は、例えば、図１～図４に示す第１保護膜付き半導体チップと同様の構成を有する。
　一方、第１保護膜付き半導体チップであると判定されない程度にＳ（Ｃ）／Ｓ（Ｓｎ）値が大きい、判定前の半導体チップ・第１保護膜積層体は、例えば、図２又は図４に示す第１保護膜付き半導体チップにおいて、バンプ上部の第１保護膜残留物の量がさらに増大したものと同様の構成を有する。 The semiconductor chip / first protective film laminate before the determination has a small S (C) / S (Sn) value to such an extent that it is determined to be the semiconductor chip with the first protective film, for example, as shown in FIGS. It has the same configuration as the semiconductor chip with a first protective film shown.
On the other hand, the semiconductor chip / first protective film laminate before the determination has a large S (C) / S (Sn) value to such an extent that it is not determined to be the semiconductor chip with the first protective film, for example, FIG. In the semiconductor chip with a first protective film shown in FIG. 5, the same configuration as that in which the amount of the first protective film residue on the bump is further increased is provided.
　以下、具体的実施例により、本発明についてより詳細に説明する。ただし、本発明は、以下に示す実施例に、何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail by way of specific examples. However, the present invention is not limited at all to the examples shown below.
　熱硬化性樹脂フィルム形成用組成物の製造に用いた成分を以下に示す。
・重合体成分（Ａ）
　重合体成分（Ａ）－１：下記式（ｉ）－１、（ｉ）－２及び（ｉ）－３で表される構成単位を有するポリビニルブチラール（積水化学工業社製「エスレックＢＬ－１０」、重量平均分子量２５０００、ガラス転移温度５９℃） The component used for manufacture of the composition for thermosetting resin film formation is shown below.
・ Polymer component (A)
Polymer component (A) -1: polyvinyl butyral having structural units represented by the following formulas (i) -1, (i) -2 and (i) -3 ("S-Lec BL-10" manufactured by Sekisui Chemical Co., Ltd.) , Weight average molecular weight 25,000, glass transition temperature 59 ° C)
Figure JPOXMLDOC01-appb-C000002
 　（式中、ｌ１は約２８であり、ｍ１は１～３であり、ｎ１は６８～７４の整数である。）
Figure JPOXMLDOC01-appb-C000002
 (Wherein, l 1 is about 28, m 1 is 1 to 3, and n 1 is an integer of 68 to 74.)
・エポキシ樹脂（Ｂ１）
　エポキシ樹脂（Ｂ１）－１：液状ビスフェノールＡ型エポキシ樹脂（ＤＩＣ社製「ＥＰＩＣＬＯＮ　ＥＸＡ－４８１０－１０００」、重量平均分子量４３００、エポキシ当量４０８ｇ／ｅｑ）
　エポキシ樹脂（Ｂ１）－２：ジシクロペンタジエン型エポキシ樹脂（ＤＩＣ社製「ＥＰＩＣＬＯＮ　ＨＰ－７２００」、分子量５５０、エポキシ当量２５４～２６４ｇ／ｅｑ）
・熱硬化剤（Ｂ２）
　熱硬化剤（Ｂ２）－１：ノボラック型フェノール樹脂（昭和電工社製「ショウノール（登録商標）ＢＲＧ－５５６」）
・硬化促進剤（Ｃ）
　硬化促進剤（Ｃ）－１：２－フェニル－４，５－ジヒドロキシメチルイミダゾール（四国化成工業社製「キュアゾール２ＰＨＺ」）
・充填材（Ｄ）
　充填材（Ｄ）－１：エポキシ基で修飾された球状シリカ（アドマテックス社製「アドマナノ　ＹＡ０５０Ｃ－ＭＫＫ」、平均粒径０．０５μｍ） ・ Epoxy resin (B1)
Epoxy resin (B1) -1: Liquid bisphenol A type epoxy resin (manufactured by DIC "EPICLON EXA-4810-1000", weight average molecular weight 4300, epoxy equivalent 408 g / eq)
Epoxy resin (B1) -2: dicyclopentadiene type epoxy resin ("EPICLON HP-7200" manufactured by DIC, molecular weight 550, epoxy equivalent 254 to 264 g / eq)
・ Heat curing agent (B2)
Thermosetting agent (B2) -1: Novolak-type phenol resin ("Shonol (registered trademark) BRG-556" manufactured by Showa Denko KK)
· Hardening accelerator (C)
Hardening accelerator (C) -1: 2-phenyl-4,5-dihydroxymethylimidazole ("Cuazole 2PHZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.)
· Filler (D)
Filler (D) -1: Spherical silica modified with epoxy group ("Adma Nano YA050C-MKK" manufactured by Admatechs, average particle size 0.05 μm)
［実施例１］
＜＜第１保護膜形成用シートの製造＞＞
＜熱硬化性樹脂フィルム形成用組成物の製造＞
　重合体成分（Ａ）－１（９．９質量部）、エポキシ樹脂（Ｂ１）－１（３７．８質量部）、エポキシ樹脂（Ｂ１）－２（２５．０質量部）、熱硬化剤（Ｂ２）－１（１８．１質量部）、硬化促進剤（Ｃ）－１（０．２質量部）及び充填材（Ｄ）－１（９．０質量部）を、メチルエチルケトンに溶解又は分散させて、２３℃で撹拌することで、熱硬化性樹脂フィルム形成用組成物として、固形分濃度が５５質量％である樹脂層形成用組成物（ＩＩＩ）を得た。なお、ここに示す各成分の配合量は、すべて固形分量である。 Example 1
<< Production of Sheet for Forming First Protective Film >>
<Production of Composition for Forming Thermosetting Resin Film>
Polymer component (A) -1 (9.9 parts by mass), epoxy resin (B1) -1 (37.8 parts by mass), epoxy resin (B1) -2 (25.0 parts by mass), thermosetting agent ( B2) -1 (18.1 parts by mass), curing accelerator (C) -1 (0.2 parts by mass) and filler (D) -1 (9.0 parts by mass) are dissolved or dispersed in methyl ethyl ketone By stirring at 23 ° C., a composition for forming a resin layer (III) having a solid content concentration of 55% by mass was obtained as a composition for forming a thermosetting resin film. In addition, the compounding quantity of each component shown here is all solid content.
＜第１保護膜形成用シートの製造＞
　ポリエチレンテレフタレート製フィルムの片面がシリコーン処理により剥離処理された剥離フィルム（リンテック社製「ＳＰ－ＰＥＴ３８１０３１」、厚さ３８μｍ）を用い、その前記剥離処理面に、上記で得られた熱硬化性樹脂フィルム形成用組成物を塗工し、１２０℃で２分加熱乾燥させることにより、厚さ３０μｍの熱硬化性樹脂フィルムを形成した。
　次いで、第１支持シートとして貼付テープ（リンテック社製「Ｅ－８５１０ＨＲ」）を用い、この貼付テープの貼付対象層に、上述の剥離フィルム上の熱硬化性樹脂フィルムを貼り合わせることで、第１支持シート、熱硬化性樹脂フィルム及び剥離フィルムがこの順に、これらの厚さ方向において積層されて構成された、図６に示す構造を有する第１保護膜形成用シートを得た。 <Production of first protective film-forming sheet>
The thermosetting resin film obtained above is used on the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Corporation, 38 μm thick) obtained by release treatment of one side of a polyethylene terephthalate film by silicone treatment. The composition for formation was applied and dried by heating at 120 ° C. for 2 minutes to form a thermosetting resin film with a thickness of 30 μm.
Then, using a sticking tape (“E-8510 HR” manufactured by Lintec Corporation) as a first support sheet, the thermosetting resin film on the above-mentioned release film is bonded to the sticking target layer of the sticking tape to obtain the first A support sheet, a thermosetting resin film, and a release film were laminated in this thickness direction in this order, to obtain a first protective film-forming sheet having a structure shown in FIG.
＜＜半導体チップ・第１保護膜積層体（第１保護膜付き半導体チップ）の製造＞＞
　上記で得られた第１保護膜形成用シートにおいて、剥離フィルムを取り除き、これにより露出した熱硬化性樹脂フィルムの表面（露出面）を、半導体ウエハのバンプ形成面に圧着させることで、半導体ウエハのバンプ形成面に第１保護膜形成用シートを貼付した。このとき、第１保護膜形成用シートの貼付は、貼付装置（ローラー式ラミネータ、リンテック社製「ＲＡＤ－３５１０　Ｆ／１２」）を用いて、テーブル温度９０℃、貼付速度２ｍｍ／ｓｅｃ、貼付圧力０．５ＭＰａの条件で、熱硬化性樹脂フィルムを加熱しながら行った。半導体ウエハとしては、バンプの形状が図１に示すように概ね球状であり、バンプの高さが２１０μｍであり、バンプの幅が２５０μｍであり、隣り合うバンプ間の距離が４００μｍであり、バンプを除いた部位の厚さが７８０μｍであるものを用いた。
　以上により、半導体ウエハのバンプ形成面に、第１保護膜形成用シートが貼付されて構成された、積層構造体（１）を得た。 << Manufacturing of semiconductor chip / first protective film laminate (semiconductor chip with first protective film) >>
In the first protective film-forming sheet obtained above, the release film is removed, and the surface (exposed surface) of the thermosetting resin film exposed thereby is pressure-bonded to the bump-formed surface of the semiconductor wafer to obtain a semiconductor wafer. A sheet for forming a first protective film was attached to the surface on which the bumps were formed. At this time, using a sticking device (roller type laminator, “RAD-3510 F / 12” manufactured by Lintec Corporation), to stick the first protective film-forming sheet, table temperature 90 ° C., sticking speed 2 mm / sec, sticking pressure It carried out, heating a thermosetting resin film on conditions of 0.5 Mpa. As a semiconductor wafer, the shape of the bumps is generally spherical as shown in FIG. 1, the height of the bumps is 210 μm, the width of the bumps is 250 μm, and the distance between adjacent bumps is 400 μm. The thickness of the removed portion was 780 μm.
Thus, a laminated structure (1) was obtained in which the first protective film-forming sheet was attached to the bump formation surface of the semiconductor wafer.
　次いで、グラインダー（ディスコ社製「ＤＧＰ８７６０」）を用いて、得られた積層構造体（１）における半導体ウエハの、バンプ形成面とは反対側の面（裏面）を研削した。このとき、半導体ウエハのバンプを除いた部位の厚さが２８０μｍとなるまで、前記裏面を研削した。 Then, using a grinder (“DGP 8760” manufactured by Disco Co., Ltd.), the surface (rear surface) opposite to the bump formation surface of the semiconductor wafer in the obtained laminated structure (1) was ground. At this time, the back surface was ground until the thickness of the portion excluding the bumps of the semiconductor wafer became 280 μm.
　次いで、紫外線照射装置（リンテック社製「ＲＡＤ－２０００　ｍ／１２」）を用いて、照度２３０ｍＷ／ｃｍ２、光量５７０ｍＪ／ｃｍ２の条件で、裏面を研削後の積層構造体（１）中の第１保護膜形成用シートに紫外線を照射した。これにより、第１保護膜形成用シート中の第１支持シートのうち、熱硬化性樹脂フィルムに接触している層を紫外線硬化させた。
　次いで、貼付装置（リンテック社製「ＲＡＤ－２７００ Ｆ／１２」）を用いて、第１支持シート（貼付シート）を積層構造体（１）中の熱硬化性樹脂フィルムから剥離させた。
　以上により、半導体ウエハのバンプ形成面に、熱硬化性樹脂フィルムを備えて構成された、積層構造体（２）（硬化性樹脂フィルム付き半導体ウエハ）を得た。 Next, using a UV irradiation apparatus ("RAD-2000 m / 12" manufactured by Lintec Corporation), the laminated structure (1) after grinding the back surface under the conditions of illuminance 230 mW / cm 2 and light quantity 570 mJ / cm 2 The first protective film forming sheet was irradiated with ultraviolet light. Thereby, the layer in contact with the thermosetting resin film in the first support sheet in the first protective film-forming sheet was cured by ultraviolet light.
Next, the first support sheet (sticking sheet) was peeled from the thermosetting resin film in the laminated structure (1) using a sticking apparatus (“RAD-2700 F / 12” manufactured by Lintec Corporation).
By the above, the laminated structure (2) (semiconductor wafer with a curable resin film), which is configured to include a thermosetting resin film on the bump formation surface of the semiconductor wafer, is obtained.
　次いで、熱硬化装置（リンテック社製「ＲＡＤ－９１００ ｍ／１２」）を用いて、加熱温度１３０℃、加熱時圧力０．５ＭＰａ、加熱時間２時間の条件で、上記で得られた積層構造体（２）中の熱硬化性樹脂フィルムを熱硬化させて、第１保護膜を形成した。
　以上により、半導体ウエハのバンプ形成面に、第１保護膜を備えて構成された、積層構造体（３）（第１保護膜付き半導体ウエハ）を得た。 Next, using the heat curing apparatus ("RAD-9100 m / 12" manufactured by Lintec Corporation), the laminated structure obtained above under the conditions of a heating temperature of 130 ° C., a heating pressure of 0.5 MPa and a heating time of 2 hours The thermosetting resin film in (2) was thermally cured to form a first protective film.
As described above, a laminated structure (3) (a semiconductor wafer with a first protective film) including the first protective film provided on the bump formation surface of the semiconductor wafer was obtained.
　次いで、プラズマ照射機（ｓａｍｃｏ社製「ＲＩＥ－１０ＮＲＴ」）を用いて、上記で得られた積層構造体（３）中の、半導体ウエハのバンプ上部に対して、プラズマを照射し、バンプ上部の第１保護膜残留物の量を低減する操作を行った。このとき、テトラフルオロメタン（ＣＦ４）ガスの流量を４０ｓｃｃｍ、酸素ガスの流量を８０ｓｃｃｍ、出力を２５０Ｗ、ガス導入後圧力を１００Ｐａとして、プラズマを１分照射した。また、このとき、プラズマは、第１保護膜を備えた半導体ウエハの、バンプを有する側の全面に、照射するようにした。
　以上により、積層構造体（４）を得た。 Next, plasma is applied to the bump upper portion of the semiconductor wafer in the laminated structure (3) obtained above using a plasma irradiator (“RIE-10 NRT” manufactured by samco), and An operation to reduce the amount of the first protective film residue was performed. At this time, the plasma was irradiated for 1 minute by setting the flow rate of tetrafluoromethane (CF 4 ) gas to 40 sccm, the flow rate of oxygen gas to 80 sccm, an output of 250 W, and a pressure of 100 Pa after gas introduction. Also, at this time, plasma was applied to the entire surface of the semiconductor wafer provided with the first protective film on the side having the bumps.
Thus, a laminated structure (4) was obtained.
　次いで、得られた積層構造体（４）中の、半導体ウエハの前記裏面（研削面）に、ダイシングテープ（リンテック社製「Ａｄｗｉｌｌ　Ｄ－６７５」）を貼付することで、半導体ウエハのバンプ形成面に第１保護膜を備え、前記裏面にダイシングテープを備えて構成された、積層構造体（５）を得た。 Then, a dicing tape ("Adwill D-675" manufactured by Lintec Corporation) is attached to the back surface (ground surface) of the semiconductor wafer in the obtained laminated structure (4) to form a bump-formed surface of the semiconductor wafer A laminated structure (5) was obtained, which was provided with the first protective film and the dicing tape on the back surface.
　次いで、ダイシング装置（ディスコ社製「ＤＦＤ６３６１」）及びダイシングブレード（ディスコ社製「ＮＢＣ－ＺＨ２０５０－２７ＨＥＣＣ」）を用いて、積層構造体（５）中の半導体ウエハを第１保護膜とともに個片化し（すなわち、積層構造体（４）を個片化し）、大きさが６ｍｍ×６ｍｍの半導体チップを形成して、積層構造体（６）を得た。 Then, using a dicing apparatus ("DFD6361" manufactured by Disco Corporation) and a dicing blade ("NBC-ZH2050-27HECC" manufactured by Disco Corporation), the semiconductor wafer in the laminated structure (5) is singulated together with the first protective film (Ie, the laminated structure (4) was singulated) to form a semiconductor chip having a size of 6 mm × 6 mm to obtain a laminated structure (6).
　次いで、紫外線照射装置（リンテック社製「ＲＡＤ－２０００　ｍ／１２」）を用いて、照度２３０ｍＷ／ｃｍ２、光量１２０ｍＪ／ｃｍ２の条件で、上記で得られた積層構造体（６）中のダイシングテープに紫外線を照射した。これにより、ダイシングテープのうち、半導体チップに接触している層を紫外線硬化させた。 Next, using the ultraviolet irradiation device ("RAD-2000 m / 12" manufactured by Lintec Corporation), in the laminated structure (6) obtained above under the conditions of an illuminance of 230 mW / cm 2 and a light amount of 120 mJ / cm 2 The dicing tape was irradiated with ultraviolet light. Thereby, the layer in contact with the semiconductor chip in the dicing tape was cured by ultraviolet light.
　次いで、半導体チップのバンプ形成面に第１保護膜を備えて構成されている半導体チップ・第１保護膜積層体を、紫外線照射後のダイシングテープから引き離してピックアップした。 Next, the semiconductor chip / first protective film laminate configured to include the first protective film on the bump formation surface of the semiconductor chip was separated from the dicing tape after the ultraviolet irradiation and picked up.
＜＜バンプの評価＞＞
＜バンプの頭頂部におけるＳ（Ｃ）／Ｓ（Ｓｎ）値＞
　上述の半導体チップ・第１保護膜積層体の製造過程において、積層構造体（６）中のダイシングテープへの紫外線照射と、半導体チップ・第１保護膜積層体のピックアップと、の間のタイミングで、半導体チップ・第１保護膜積層体中のバンプの頭頂部について、ＥＤＸによって分析を行い、Ｓ（Ｃ）／Ｓ（Ｓｎ）値を求めた。分析対象である半導体チップ・第１保護膜積層体の、ダイシングテープ上での配置位置を説明するための平面図を図１１に示す。図１１に示すように、ダイシングテープ８上には、１４４個の半導体チップ・第１保護膜積層体１’が配置されている。これらのうち、符号１’－１～１’－６を付した６個の半導体チップ・第１保護膜積層体１’について、ＥＤＸ分析を行った。ＥＤＸ分析は、バンプの頂上を含む上部領域を対象として行った。前記上部領域は、バンプをその上方から見下ろして平面視したときに、バンプの頂上を含み、かつ、直径が１００μｍである円形領域として認識される領域、とした。すなわち、この円形領域をＥＤＸでの走査範囲とした。そして、得られたＳ（Ｃ）／Ｓ（Ｓｎ）値の平均値を、本実施例でのＳ（Ｃ）／Ｓ（Ｓｎ）値として採用した。
　ＥＤＸ分析は、電界放出形走査電子顕微鏡（日立ハイテクノロジーズ社製「ＦＥ－ＳＥＭ　Ｓ－４７００」）を用いて、加速電圧２０ｋＶ、レンズ－試料間距離１２ｍｍの条件で行った。結果を、表１中の「Ｓ（Ｃ）／Ｓ（Ｓｎ）値」の欄に示す。 << Bump evaluation >>
<S (C) / S (Sn) value at the top of the bump>
In the manufacturing process of the above semiconductor chip / first protective film laminate, at the timing between the irradiation of ultraviolet light to the dicing tape in the laminate structure (6) and the pickup of the semiconductor chip / first protective film laminate The top of the bump in the semiconductor chip / first protective film laminate was analyzed by EDX to determine the S (C) / S (Sn) value. FIG. 11 is a plan view for explaining the arrangement position on the dicing tape of the semiconductor chip-first protective film laminate to be analyzed. As shown in FIG. 11, 144 semiconductor chip / first protective film laminates 1 ′ are disposed on the dicing tape 8. Among these, EDX analysis was performed on six semiconductor chip / first protective film laminates 1 ′ denoted by reference numerals 1′-1 to 1′-6. EDX analysis was performed on the upper area including the top of the bump. The upper area is an area recognized as a circular area including the top of the bump and having a diameter of 100 μm when the bump is viewed from above and viewed in plan from above. That is, this circular area was made into the scanning range in EDX. Then, the average value of the obtained S (C) / S (Sn) values was adopted as the S (C) / S (Sn) value in this example.
EDX analysis was performed using a field emission scanning electron microscope ("FE-SEM S-4700" manufactured by Hitachi High-Technologies Corporation) under the conditions of an acceleration voltage of 20 kV and a lens-sample distance of 12 mm. The results are shown in the column of “S (C) / S (Sn) value” in Table 1.
＜銅板と半導体チップとの接合体におけるせん断破壊形態＞
　上記で得られた、ピックアップ後の半導体チップ・第１保護膜積層体を、フラックスが塗布された銅板（厚さ３００μｍ）の表面に載置し、２６０℃で２分加熱することにより、この銅板に接合した。このとき、半導体チップ・第１保護膜積層体中のバンプが銅板の表面に接触するようにした。そして、銅板を洗浄してフラックスを除去した。
　次いで、せん断力測定装置（ｎｏｒｄｓｏｎ　Ｄａｇｅ社製「Ｄａｇｅ－ＳＥＲＩＥＳ４０００ＸＹ」）を用いて、接合された半導体チップ・第１保護膜積層体に、銅板の表面（半導体チップ・第１保護膜積層体が接合されている面）に対して並行な方向にせん断力を加えて、接合状態を破壊した。そして、その破壊部位を観察して、破壊が「バンプ及び銅板間の界面における界面破壊（以下、単に「界面破壊」と略記する）」と、「バンプの破壊（以下、「凝集破壊」と略記する）」と、のいずれであるかを判定した。結果を、表１中の「せん断破壊形態」の欄に示す。 <Shear fracture form in the joint of copper plate and semiconductor chip>
The above obtained semiconductor chip / first protective film laminate after pickup is placed on the surface of a copper plate (thickness 300 μm) coated with flux, and this copper plate is heated at 260 ° C. for 2 minutes. Bonded to At this time, the bumps in the semiconductor chip / first protective film laminate were in contact with the surface of the copper plate. Then, the copper plate was washed to remove the flux.
Next, the surface of the copper plate (the semiconductor chip and the first protective film laminate is joined to the semiconductor chip and the first protective film laminate joined using the shear force measuring apparatus (“Dage-SERIES 4000XY” manufactured by nordson Dage) The joint was broken by applying a shear force parallel to the surface). Then, observing the fracture site, the fracture is “interface fracture at the interface between the bump and the copper plate (hereinafter simply referred to as“ interface fracture ”)” and “bump fracture (hereinafter“ cohesive fracture ”) It was determined whether it was "or". The results are shown in the column of “shear failure form” in Table 1.
＜基板と半導体チップとの接合体における電気的接続度＞
　上記で得られた、ピックアップ後の半導体チップ・第１保護膜積層体を、フラックスが塗布された基板（ＫＩＴ　ＷＬＰ（ｓ）　３００Ｐ／４００Ｐ、厚さ１０００μｍ）の表面に載置し、３５０℃で２分加熱することにより、この基板に接合した。このとき、半導体チップ・第１保護膜積層体中のバンプが前記基板の表面に接触するようにした。そして、基板を洗浄してフラックスを除去した。
　次いで、テスター（ＨＩＯＫＩ製「３４２２　ＨｉＣＡＲＤＴＥＳＴＥＲ」）を用いて、半導体チップと基板との間の抵抗値を測定した。そして、抵抗値が２．７～３．０Ωである場合には、電気的接続度をＡ（良好）と判定し、抵抗値が２．７～３．０Ωの範囲から外れる場合には、電気的接続度をＢ（不良）と判定した。結果を、表１中の「電気的接続度」の欄に示す。 <The degree of electrical connection in the joined body of the substrate and the semiconductor chip>
The semiconductor chip / first protective film laminate after pickup obtained above is placed on the surface of a substrate (KIT WLP (s) 300 P / 400 P, thickness 1000 μm) coated with flux, and it is at 350 ° C. The substrate was bonded by heating for 2 minutes. At this time, the bumps in the semiconductor chip-first protective film laminate were in contact with the surface of the substrate. The substrate was then cleaned to remove the flux.
Next, a resistance value between the semiconductor chip and the substrate was measured using a tester (“3422 HiCARDTESTER” manufactured by HIOKI). Then, when the resistance value is 2.7 to 3.0 Ω, the degree of electrical connection is determined as A (good), and when the resistance value is out of the range of 2.7 to 3.0 Ω, The target connectivity was determined to be B (defect). The results are shown in the column of “degree of electrical connection” in Table 1.
［実施例２］
＜＜第１保護膜形成用シートの製造＞＞
　実施例１の場合と同じ方法で、第１保護膜形成用シートを製造した。 Example 2
<< Production of Sheet for Forming First Protective Film >>
In the same manner as in Example 1, a sheet for forming a first protective film was produced.
＜＜半導体チップ・第１保護膜積層体（第１保護膜付き半導体チップ）の製造＞＞
　実施例１の場合と同じ方法で、積層構造体（３）（第１保護膜付き半導体ウエハ）を製造した。 << Manufacturing of semiconductor chip / first protective film laminate (semiconductor chip with first protective film) >>
The laminated structure (3) (semiconductor wafer with first protective film) was manufactured in the same manner as in Example 1.
　次いで、得られた積層構造体（３）中の、半導体ウエハの前記裏面（研削面）に、ダイシングテープ（リンテック社製「Ａｄｗｉｌｌ　Ｄ－６７５」）を貼付することで、半導体ウエハのバンプ形成面に第１保護膜を備え、前記裏面にダイシングテープを備えて構成された、積層構造体（７）を得た。 Then, a dicing tape ("Adwill D-675" manufactured by Lintec Corporation) is attached to the back surface (grind surface) of the semiconductor wafer in the obtained laminated structure (3) to form a bump-formed surface of the semiconductor wafer A laminated structure (7) was obtained, which was provided with the first protective film and the dicing tape on the back surface.
　次いで、ダイシング装置（ディスコ社製「ＤＦＤ６３６１」）及びダイシングブレード（ディスコ社製「ＮＢＣ－ＺＨ２０５０－ＳＥ　２７ＨＥＥＦ」）を用いて、ブレード回転数３００００ｒｐｍ、ブレード送り速度５０ｍｍ／ｓの条件で、バンプをその頂点から５０μｍだけ下の部位において、バンプ形成面に対して平行な方向において切断し、切断片を除去した。このように、バンプ上部の第１保護膜残留物の量を低減する操作を行うことにより、バンプを、高さが１６０μｍであり、かつ、頭頂部が平面状である点以外は、実施例１の場合と同じであるものとした。換言すると、本実施例では、バンプの形状を図３に示すものとした。得られた積層構造体（８）は、さらに、ダイシング装置の洗浄ユニットを用いて洗浄した。 Next, using a dicing apparatus (Docco “DFD6361”) and a dicing blade (“NBC-ZH2050-SE 27 HEEF” manufactured by Disco), the bumps were processed under conditions of a blade rotational speed of 30,000 rpm and a blade feed speed of 50 mm / s. At a portion 50 μm below the apex, cutting was performed in a direction parallel to the bump formation surface to remove a cut piece. Thus, by performing an operation to reduce the amount of the first protective film residue on the upper portion of the bump, the bump has a height of 160 μm and the head is flat except for the example 1 The same as in the case of In other words, in the present embodiment, the shape of the bumps is as shown in FIG. The obtained laminated structure (8) was further washed using the washing unit of the dicing apparatus.
　次いで、上述の積層構造体（５）に代えて、上記で得られた積層構造体（８）を用い、実施例１の場合と同じ方法で、積層構造体（８）中の半導体ウエハを第１保護膜とともに個片化し、大きさが６ｍｍ×６ｍｍの半導体チップを形成することにより、積層構造体（９）を得た。 Then, in place of the above-described laminated structure (5), using the laminated structure (8) obtained above, the semiconductor wafer in the laminated structure (8) is manufactured in the same manner as in Example 1. A laminated structure (9) was obtained by singulating together with 1 protective film and forming a semiconductor chip having a size of 6 mm × 6 mm.
　次いで、上述の積層構造体（６）に代えて、上記で得られた積層構造体（９）を用い、積層構造体（９）中のダイシングテープに紫外線を照射した。これにより、ダイシングテープのうち、半導体チップに接触している層を紫外線硬化させた。 Next, the dicing tape in the laminated structure (9) was irradiated with ultraviolet light using the laminated structure (9) obtained above in place of the laminated structure (6) described above. Thereby, the layer in contact with the semiconductor chip in the dicing tape was cured by ultraviolet light.
　次いで、実施例１の場合と同じ方法で、半導体チップのバンプ形成面に第１保護膜を備えて構成されている半導体チップ・第１保護膜積層体を、紫外線照射後のダイシングテープから、引き離してピックアップした。 Then, in the same manner as in Example 1, the semiconductor chip / first protective film laminate configured to have the first protective film on the bump formed surface of the semiconductor chip is separated from the dicing tape after the ultraviolet irradiation. I picked it up.
＜＜バンプの評価＞＞
　上記で得られた半導体チップ・第１保護膜積層体について、実施例１の場合と同じ方法で、バンプを評価した。結果を表１に示す。 << Bump evaluation >>
Bumps were evaluated in the same manner as in Example 1 for the semiconductor chip-first protective film laminate obtained above. The results are shown in Table 1.
＜＜半導体チップの製造、バンプの評価＞＞
［参考例１］
＜＜半導体チップの製造＞＞
　上述の剥離フィルムを取り除いた第１保護膜形成用シートに代えて、貼付テープ（リンテック社製「Ｅ－８５１０ＨＲ」）を用いた点以外は、実施例１の場合と同じ方法で、半導体ウエハのバンプ形成面に前記貼付テープが貼付されて構成された、積層構造体（１Ｒ）を得た。 << Production of semiconductor chips, evaluation of bumps >>
[Reference Example 1]
<< Manufacturing of semiconductor chips >>
A semiconductor wafer is manufactured in the same manner as in Example 1 except that a sticking tape ("E-8510 HR" manufactured by Lintec Corporation) is used instead of the first protective film-forming sheet from which the above-described release film has been removed. A laminated structure (1R) was obtained in which the sticking tape was attached to the bump formation surface.
　次いで、上述の積層構造体（１）に代えて、上記で得られた積層構造体（１Ｒ）を用いた点以外は、実施例１の場合と同じ方法で、積層構造体（１Ｒ）における半導体ウエハについて、そのバンプを除いた部位の厚さが２８０μｍとなるまで、裏面を研削した。
　次いで、半導体ウエハの前記裏面（研削面）に、ダイシングテープ（リンテック社製「Ａｄｗｉｌｌ　Ｄ－６７５」）を貼付して、積層構造体（２Ｒ）を得た。 Next, the semiconductor in the laminated structure (1R) is the same method as in Example 1 except that the laminated structure (1R) obtained above is used instead of the above-mentioned laminated structure (1) The backside of the wafer was ground until the thickness of the portion excluding the bumps was 280 μm.
Next, a dicing tape (“Adwill D-675” manufactured by Lintec Corporation) was attached to the back surface (ground surface) of the semiconductor wafer to obtain a laminated structure (2R).
　次いで、上述の裏面を研削後の積層構造体（１）に代えて、上記で得られた積層構造体（２Ｒ）を用いた点以外は、実施例１の場合と同じ方法で、貼付テープに紫外線を照射した。これにより、貼付テープのうち、半導体ウエハのバンプ形成面に接触している層を紫外線硬化させた。
　次いで、実施例１の場合と同じ方法で、貼付シートを半導体ウエハから剥離させた。
　以上により、半導体ウエハのバンプ形成面は露出しており、半導体ウエハの裏面にダイシングテープを備えて構成された、積層構造体（３Ｒ）（すなわち、ダイシングテープ付き半導体ウエハ）を得た。 Then, in place of the laminated structure (1) after grinding on the back surface described above, using the laminated structure (2R) obtained above, in the same manner as in the case of Example 1, to attach an adhesive tape It was irradiated with ultraviolet light. Thus, the layer of the adhesive tape in contact with the bump formation surface of the semiconductor wafer was ultraviolet-cured.
Subsequently, the sticking sheet was peeled from the semiconductor wafer in the same manner as in Example 1.
From the above, the bump formation surface of the semiconductor wafer was exposed, and a laminated structure (3R) (that is, a semiconductor wafer with a dicing tape) configured by providing a dicing tape on the back surface of the semiconductor wafer was obtained.
　次いで、上述の積層構造体（５）に代えて、上記で得られた積層構造体（３Ｒ）を用いた点以外は、実施例１の場合と同じ方法で、積層構造体（３Ｒ）中の半導体ウエハを個片化し、大きさが６ｍｍ×６ｍｍの半導体チップを形成することにより、積層構造体（４Ｒ）を得た。 Next, in the same manner as in Example 1, except that the above-described laminated structure (3R) was used instead of the above-mentioned laminated structure (5), in the laminated structure (3R) The semiconductor wafer was singulated to form a semiconductor chip having a size of 6 mm × 6 mm to obtain a laminated structure (4R).
　次いで、上述の積層構造体（６）に代えて、上記で得られた積層構造体（４Ｒ）を用いた点以外は、実施例１の場合と同じ方法で、積層構造体（４Ｒ）中のダイシングテープに紫外線を照射した。これにより、ダイシングテープのうち、半導体チップに接触している層を紫外線硬化させた。 Then, in the same manner as in Example 1, except that the above-described laminated structure (4R) was used instead of the above-described laminated structure (6), the conditions in the laminated structure (4R) were used. The dicing tape was irradiated with ultraviolet light. Thereby, the layer in contact with the semiconductor chip in the dicing tape was cured by ultraviolet light.
　次いで、半導体チップを、紫外線照射後ダイシングテープから、引き離してピックアップした。 Next, the semiconductor chip was separated from the dicing tape after ultraviolet irradiation and picked up.
＜＜バンプの評価＞＞
　上記で得られた半導体チップについて、実施例１の場合と同じ方法で、バンプを評価した。結果を表１に示す。 << Bump evaluation >>
The bumps of the semiconductor chip obtained above were evaluated in the same manner as in Example 1. The results are shown in Table 1.
＜＜第１保護膜形成用シートの製造、半導体チップ・第１保護膜積層体（第１保護膜付き半導体チップ）の製造、バンプの評価＞＞
［比較例１］
　実施例１の場合と同じ方法で、第１保護膜形成用シートを製造した。
　そして、積層構造体（３）中の半導体ウエハのバンプ上部に対して、プラズマを照射しなかった点以外は、実施例１の場合と同じ方法で、半導体チップ・第１保護膜積層体を製造し、バンプを評価した。結果を表１に示す。 << Manufacture of sheet for forming first protective film, manufacture of semiconductor chip / first protective film laminate (semiconductor chip with first protective film), evaluation of bumps >>
Comparative Example 1
In the same manner as in Example 1, a sheet for forming a first protective film was produced.
Then, the semiconductor chip / first protective film laminate is manufactured in the same manner as in Example 1 except that the upper part of the bump of the semiconductor wafer in the laminate structure (3) is not irradiated with plasma. And evaluated the bumps. The results are shown in Table 1.
［比較例２］
　実施例１の場合と同じ方法で、第１保護膜形成用シートを製造した。
　そして、積層構造体（３）中の半導体ウエハのバンプ上部に対して、プラズマを照射する時間を１分に代えて０．１分とした点以外は、実施例１の場合と同じ方法で、半導体チップ・第１保護膜積層体を製造し、バンプを評価した。結果を表１に示す。 Comparative Example 2
In the same manner as in Example 1, a sheet for forming a first protective film was produced.
Then, in the same manner as in Example 1, except that the time for irradiating plasma to the bump upper portion of the semiconductor wafer in the laminated structure (3) is changed to 1 minute instead of 1 minute, A semiconductor chip / first protective film laminate was manufactured, and bumps were evaluated. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　上記結果から明らかなように、実施例１～２の半導体チップ・第１保護膜積層体においては、Ｓ（Ｃ）／Ｓ（Ｓｎ）値が０．２４以下（０．０７～０．２４）となっており、バンプの頭頂部において第１保護膜残留物の量が少なかった。これは、半導体チップ・第１保護膜積層体の製造時に、実施例１においては、半導体ウエハのバンプ上部にプラズマを１分照射することにより、前記残留物低減工程を行い、実施例２においては、バンプの上部を除去することにより、前記残留物低減工程を行ったためである。 As apparent from the above results, in the semiconductor chip / first protective film laminate of Examples 1 and 2, the S (C) / S (Sn) value is 0.24 or less (0.07 to 0.24). And the amount of the first protective film residue was small at the top of the bump. This is because the residue reduction step is performed in Example 1 by irradiating plasma on the bumps of the semiconductor wafer for one minute in the production of the semiconductor chip / first protective film laminate, and in Example 2, The reason is that the residue reduction process is performed by removing the upper part of the bump.
　これら実施例では、このような結果を反映して、銅板とバンプとの間の接合強度が高く、銅板と半導体チップとの接合体におけるせん断破壊は、凝集破壊（バンプの破壊）であった。また、基板と半導体チップとの接合体における電気的接続度も高かった。 In these examples, reflecting these results, the bonding strength between the copper plate and the bump was high, and the shear failure in the bonded body of the copper plate and the semiconductor chip was cohesive failure (breaking of the bump). In addition, the degree of electrical connection in the joined body of the substrate and the semiconductor chip was also high.
　以上の結果から、実施例１～２で製造された半導体チップ・第１保護膜積層体は、目的とする第１保護膜付き半導体チップであると判定できた。 From the above results, it can be determined that the semiconductor chip / first protective film laminate manufactured in Examples 1 and 2 is the target semiconductor chip with a first protective film.
　参考例１の半導体ウエハ及び半導体チップにおいては、第１保護膜を設けておらず、Ｓ（Ｃ）／Ｓ（Ｓｎ）値が高くなる要因がなく、実際にＳ（Ｃ）／Ｓ（Ｓｎ）値は、低水準であった。
　実施例１～２、特に実施例２における上述の評価結果は、参考例１における評価結果と同等程度の水準にあり、実施例１～２では、バンプの頭頂部における第１保護膜残留物の量の低減効果が高いと判断できた。 In the semiconductor wafer and the semiconductor chip of the reference example 1, the first protective film is not provided, there is no factor that the S (C) / S (Sn) value becomes high, and in fact S (C) / S (Sn) The value was low.
The evaluation results described above in Examples 1 and 2, particularly in Example 2, are on the same level as the evaluation results in Reference Example 1. In Examples 1 and 2, the first protective film residue at the top of the bump is It was judged that the reduction effect of the amount was high.
　これに対して、比較例１の半導体チップ・第１保護膜積層体においては、前記残留物低減工程を行っていないことにより、実施例１～２の場合と比較して、Ｓ（Ｃ）／Ｓ（Ｓｎ）値が顕著に高かった。
　本比較例では、このような結果を反映して、銅板とバンプとの間の接合強度が低く、銅板と半導体チップとの接合体におけるせん断破壊は、界面破壊（バンプ及び銅板間での界面破壊）であった。また、基板と半導体チップとの接合体における電気的接続度も低かった。 On the other hand, in the semiconductor chip / first protective film laminate of Comparative Example 1, S (C) /, as compared with the cases of Examples 1 and 2, because the residue reduction step is not performed. The S (Sn) value was remarkably high.
In this comparative example, the bond strength between the copper plate and the bump is low reflecting the above result, and the shear failure in the bonded body of the copper plate and the semiconductor chip is an interface failure (interface failure between the bump and the copper plate )Met. In addition, the degree of electrical connection in the bonded body of the substrate and the semiconductor chip was also low.
　比較例２の半導体チップ・第１保護膜積層体においては、Ｓ（Ｃ）／Ｓ（Ｓｎ）値が０．３３となっており、バンプの頭頂部において第１保護膜残留物の量が多かった。これは、半導体チップ・第１保護膜積層体の製造時において、半導体ウエハのバンプ上部に対するプラズマの照射時間が短く、バンプ上部の第１保護膜残留物の量の低減が不十分であったためである。
　本比較例では、このような結果を反映して、銅板とバンプとの間の接合強度は高かったものの、基板と半導体チップとの接合体における電気的接続度が低かった。 In the semiconductor chip / first protective film laminate of Comparative Example 2, the S (C) / S (Sn) value is 0.33, and the amount of the first protective film residue is large at the top of the bump. The This is because, during the production of the semiconductor chip / first protective film laminate, the irradiation time of plasma to the bump upper portion of the semiconductor wafer is short, and the reduction of the amount of the first protective film residue on the bump upper portion is insufficient. is there.
In the present comparative example, although the bond strength between the copper plate and the bump was high reflecting such results, the degree of electrical connection in the bonded body of the substrate and the semiconductor chip was low.
　以上の結果から、比較例１～２で製造された半導体チップ・第１保護膜積層体は、目的とする第１保護膜付き半導体チップではないと判定できた。 From the above results, it can be determined that the semiconductor chip / first protective film laminate manufactured in Comparative Examples 1 and 2 is not the target semiconductor chip with a first protective film.
　本発明は、フリップチップ実装時に使用される、接続パッド部にバンプを有する半導体チップ等の製造に利用可能である。 The present invention can be used to manufacture a semiconductor chip or the like having bumps in the connection pad portion, which is used in flip chip mounting.
　１，２，３，４・・・第１保護膜付き半導体チップ（半導体チップ・第１保護膜積層体）、１’・・・半導体チップ・第１保護膜積層体、９・・・半導体チップ、９’・・・半導体ウエハ、９ａ・・・半導体チップ（半導体ウエハ）のバンプ形成面、９１，９２・・・半導体チップ（半導体ウエハ）のバンプ、９１ａ，９２ａ・・・バンプの表面、９１０，９２０・・・バンプの頭頂部、１３・・・第１保護膜、１３１・・・第１保護膜残留物、１３’・・・硬化性樹脂フィルム、１３１’・・・硬化性樹脂フィルム残留物 1, 2, 3, 4 · · · Semiconductor chip with first protective film (semiconductor chip · first protective film laminate), 1 '· · · semiconductor chip · first protective film laminate, 9 · · · semiconductor chip 9, 9 ': semiconductor wafer, 9a: bump forming surface of semiconductor chip (semiconductor wafer) 91, 92: bump of semiconductor chip (semiconductor wafer) 91a, 92a: surface of bump 910 , 920: head of bump, 13: first protective film, 131: first protective film residue, 13 ′: curable resin film, 131 ′: curable resin film remaining object

Claims (3)

  1. 　半導体チップと、前記半導体チップのバンプを有する面に形成された第１保護膜と、を備え、
    　前記バンプの頭頂部について、エネルギー分散型Ｘ線分光法によって分析を行い、炭素の検出シグナルの強度Ｓ（Ｃ）と、スズの検出シグナルの強度Ｓ（Ｓｎ）と、を測定したとき、Ｓ（Ｃ）／Ｓ（Ｓｎ）の値が０．３２以下となる、第１保護膜付き半導体チップ。     A semiconductor chip, and a first protective film formed on the surface of the semiconductor chip having a bump,
    The top of the bump is analyzed by energy dispersive X-ray spectroscopy, and the intensity S (C) of the carbon detection signal and the intensity S (Sn) of the tin detection signal are measured as follows: C) A semiconductor chip with a first protective film, in which the value of / S (Sn) is 0.32 or less.
  2. 　請求項１に記載の第１保護膜付き半導体チップの製造方法であって、
    　半導体ウエハのバンプを有する面に、硬化性樹脂フィルムを貼付する工程と、
    　貼付後の前記硬化性樹脂フィルムを硬化させることにより、第１保護膜を形成する工程と、
    　前記半導体ウエハを分割することにより、半導体チップを得る工程と、
    を有し、
    　前記硬化性樹脂フィルムを貼付する工程において、前記Ｓ（Ｃ）／Ｓ（Ｓｎ）の値が０．３２以下となるように、前記バンプの頭頂部を前記硬化性樹脂フィルムから突出させるか、又は、
    　前記硬化性樹脂フィルムを貼付する工程の後に、さらに、前記Ｓ（Ｃ）／Ｓ（Ｓｎ）の値が０．３２以下となるように、前記バンプ上の残留物の量を低減する工程を有する、第１保護膜付き半導体チップの製造方法。     A method of manufacturing a semiconductor chip with a first protective film according to claim 1, wherein
    Attaching a curable resin film to the surface of the semiconductor wafer having the bumps;
    Forming a first protective film by curing the curable resin film after application;
    Obtaining a semiconductor chip by dividing the semiconductor wafer;
    Have
    In the step of attaching the curable resin film, the top of the bump is made to protrude from the curable resin film so that the value of S (C) / S (Sn) is 0.32 or less, or ,
    After the step of attaching the curable resin film, the method further includes the step of reducing the amount of residue on the bump so that the value of S (C) / S (Sn) is 0.32 or less. And a method of manufacturing a semiconductor chip with a first protective film.
  3. 　半導体チップと、前記半導体チップのバンプを有する面に形成された第１保護膜と、を備えた、半導体チップ・第１保護膜積層体の評価方法であって、
    　前記半導体チップ・第１保護膜積層体中の前記バンプの頭頂部について、エネルギー分散型Ｘ線分光法によって分析を行い、炭素の検出シグナルの強度Ｓ（Ｃ）と、スズの検出シグナルの強度Ｓ（Ｓｎ）と、を測定し、Ｓ（Ｃ）／Ｓ（Ｓｎ）の値が０．３２以下である場合には、前記半導体チップ・第１保護膜積層体を、目的とする第１保護膜付き半導体チップであると判定し、Ｓ（Ｃ）／Ｓ（Ｓｎ）の値が０．３２よりも大きい場合には、前記半導体チップ・第１保護膜積層体を、目的とする第１保護膜付き半導体チップではないと判定する、半導体チップ・第１保護膜積層体の評価方法。     A method of evaluating a semiconductor chip / first protective film laminate, comprising: a semiconductor chip; and a first protective film formed on a surface of the semiconductor chip having bumps.
    The top of the bump in the semiconductor chip / first protective film stack is analyzed by energy dispersive X-ray spectroscopy, and the intensity S (C) of the detection signal of carbon and the intensity S of the detection signal of tin (Sn) is measured, and if the value of S (C) / S (Sn) is 0.32 or less, the semiconductor chip / first protective film laminate is used as a target first protective film When it is determined that the semiconductor chip has a chip and the value of S (C) / S (Sn) is larger than 0.32, the semiconductor chip / first protective film laminate is used as a target first protective film Evaluation method of the semiconductor chip / first protective film laminate, which is determined not to be a semiconductor chip with a chip.
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