WO2022163260A1 - 構造体、異方導電性部材の製造方法、及び保護層形成用組成物 - Google Patents

構造体、異方導電性部材の製造方法、及び保護層形成用組成物 Download PDF

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Publication number
WO2022163260A1
WO2022163260A1 PCT/JP2021/048168 JP2021048168W WO2022163260A1 WO 2022163260 A1 WO2022163260 A1 WO 2022163260A1 JP 2021048168 W JP2021048168 W JP 2021048168W WO 2022163260 A1 WO2022163260 A1 WO 2022163260A1
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Prior art keywords
protective layer
insulating film
layer
resin layer
metal
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PCT/JP2021/048168
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English (en)
French (fr)
Japanese (ja)
Inventor
吉則 堀田
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2022578178A priority Critical patent/JPWO2022163260A1/ja
Priority to CN202180092075.5A priority patent/CN116830391A/zh
Publication of WO2022163260A1 publication Critical patent/WO2022163260A1/ja
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors

Definitions

  • a plurality of conductors penetrating in the thickness direction of an insulating film and electrically insulated from each other are formed by: a resin layer covering at least one surface of the insulating film in the thickness direction;
  • the present invention relates to a structure provided with a protective layer made of an organic substance, a method for producing an anisotropically conductive member, and a composition for forming a protective layer.
  • the anisotropic conductive member is inserted between electronic parts such as semiconductor elements and the circuit board, and can be electrically connected between the electronic parts and the circuit board simply by applying pressure. It is widely used as an electrical connection member, an inspection connector, etc. when performing a function inspection. In particular, electronic parts such as semiconductor devices are undergoing remarkable downsizing. In some cases, it is not possible to sufficiently guarantee the stability of the electrical connection of electronic components by methods such as conventional wire bonding that directly connects wiring boards, flip chip bonding, and thermocompression bonding. An anisotropic conductive member has attracted attention as a connecting member.
  • Patent Document 1 discloses an insulating base material, a plurality of conductive paths made of a conductive member, and a resin layer provided on the entire surface of the insulating base material.
  • An anisotropically conductive joint member is described.
  • the resin layer contains a thermosetting resin.
  • the conduction paths are provided so as to pass through the insulating substrate in the thickness direction while being insulated from each other.
  • the conducting path has a protruding portion protruding from the surface of the insulating base material, and the end of the protruding portion is embedded in the resin layer.
  • the anisotropically conductive bonding member of Patent Document 1 in the structure in which the resin layer is provided on the entire surface of the insulating base material, the anisotropically conductive bonding member is separated into individual pieces by cutting such as dicing. At that time, chips are generated from the anisotropically conductive joint member.
  • the anisotropically conductive member that has been singulated is inserted, for example, between the semiconductor element, the electronic component, and the circuit board. Shavings become a physical obstacle when joining by hand. Therefore, it is necessary to remove the chips from the resin layer in the anisotropically conductive member that has been separated into individual pieces. However, it turned out that it is difficult to remove the cutting waste adhering to the resin layer. For this reason, it is desired to suppress the influence of cutting waste when singulating an anisotropically conductive member by cutting such as dicing.
  • An object of the present invention is to provide a structure that suppresses the influence of chips generated by cutting such as dicing, a method for manufacturing an anisotropically conductive member, and a composition for forming a protective layer.
  • one embodiment of the present invention provides an insulating film, a plurality of conductors penetrating the insulating film in a thickness direction and electrically insulated from each other, and an insulating film. It has a resin layer covering at least one surface in the thickness direction and a protective layer made of an organic material, the resin layer being provided between the insulating film and the protective layer, and the protective layer being the outermost surface layer. , which provides a structure.
  • the protective layer preferably has oxygen barrier properties. It is preferable that the protective layer and the resin layer are in direct contact.
  • the protective layer preferably has an adhesion of 2 to 10 N/25 mm to other layers in contact with it.
  • the protective layer is subjected to dissolution removal with a remover, and the remover preferably contains a solvent having a dissolution rate of 1 ⁇ m/s or more for the protective layer at a temperature of 25°C.
  • the removing liquid preferably contains ethyl acetate.
  • the conductor preferably protrudes from at least one surface in the thickness direction of the insulating film. Preferably, the conductor protrudes from both sides of the insulating film in the thickness direction.
  • the insulating film is preferably composed of an anodized film.
  • an insulating film in another aspect of the present invention, an insulating film, a plurality of conductors penetrating the insulating film in the thickness direction and electrically insulated from each other, and at least one surface of the insulating film in the thickness direction are provided. It has a covering resin layer and a protective layer made of an organic substance, wherein the resin layer is provided between the insulating film and the protective layer, and the protective layer is an anisotropically conductive structure using a structure that is the outermost layer.
  • a method for manufacturing an anisotropically conductive member which includes a removing step for removing a protective layer.
  • the insulating film is preferably composed of an anodized film.
  • Another aspect of the present invention provides a composition for forming a protective layer, which constitutes the protective layer of the structure of the present invention, and which contains a resin.
  • the structure of the present invention it is possible to suppress the influence of shavings during singulation.
  • the method for manufacturing an anisotropically conductive member of the present invention it is possible to obtain an anisotropically conductive member that can suppress the influence of cutting waste during singulation.
  • the composition for forming a protective layer of the present invention it is possible to obtain a protective layer capable of suppressing the influence of shavings during singulation.
  • FIG. 1 is a schematic cross-sectional view showing an example of a structure according to an embodiment of the invention
  • FIG. 1 is a schematic plan view showing an example of a structure according to an embodiment of the invention
  • FIG. 4 is a schematic cross-sectional view showing an example of cutting the structure of the embodiment of the present invention
  • FIG. 4 is a schematic cross-sectional view showing an example of cutting the structure of the embodiment of the present invention
  • FIG. 4 is a schematic cross-sectional view showing an example of cutting the structure of the embodiment of the present invention
  • 1 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a structure according to an embodiment of the present invention
  • FIG. 1 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a structure according to an embodiment of the present invention
  • FIG. 1 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a structure according to an embodiment of the present invention
  • FIG. 1 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a structure according to an embodiment of the present invention
  • FIG. 1 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a structure according to an embodiment of the present invention
  • FIG. 1 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a structure according to an embodiment of the present invention
  • FIG. 1 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a structure according to an embodiment of the present invention
  • FIG. 1 is a schematic cross-sectional view showing one step of an example of a method for manufacturing a structure according to an embodiment of
  • FIG. 1 is a schematic cross-sectional view showing an example of a fine structure according to an embodiment of the present invention
  • FIG. 2 is a schematic plan view showing an example of a fine structure according to an embodiment of the present invention
  • FIG. 2 is a plan view of the insulating film of FIG. 1 as viewed from the surface side, showing a state without the resin layer 20 and the protective layer 22.
  • FIG. The structure 10 shown in FIG. 1 includes an insulating film 12 having electrical insulation properties, and a plurality of conductors 14 that penetrate through the insulating film 12 in the thickness direction Dt and are electrically insulated from each other. have
  • the plurality of conductors 14 are arranged in the insulating film 12 in a state of being electrically insulated from each other.
  • the insulating film 12 has a plurality of pores 13 penetrating in the thickness direction Dt.
  • Conductors 14 are provided in the plurality of pores 13 .
  • the conductor 14 protrudes from the surface 12a of the insulating film 12 in the thickness direction Dt.
  • the conductor 14 protrudes from the back surface 12b of the insulating film 12 in the thickness direction Dt.
  • An anisotropic conductive layer 16 is formed by the insulating film 12 and the plurality of conductors 14 .
  • the structure 10 has a resin layer 20 covering at least one surface of the insulating film 12 in the thickness direction Dt.
  • the resin layer 20 is provided on the entire front surface 12a and the entire rear surface 12b of the insulating film 12, respectively.
  • the insulating film 12 is composed of, for example, an anodized film 15 .
  • the resin layer 20 covers the protruding conductors 14 .
  • the resin layer 20 covers the projecting portion 14 a of the conductor 14 , and the projecting portion 14 a is embedded in the resin layer 20 .
  • the resin layer 20 covers the projecting portion 14 b of the conductor 14 , and the projecting portion 14 b is embedded in the resin layer 20 .
  • the structure 10 has a protective layer 22 made of organic material.
  • the resin layer 20 is provided between the insulating film 12 and the protective layer 22 .
  • the protective layer 22 is provided on the surface 20a of the resin layer 20 in direct contact therewith.
  • the surface 20 a of the resin layer 20 is the surface opposite to the insulating film 12 .
  • the protective layer 22 is provided on the front surface 12a side and the rear surface 12b side of the insulating film 12, respectively.
  • the protective layer 22 is the outermost layer of the structure 10 .
  • the protective layer 22 protects the resin layer 20 and prevents chips and the like from adhering to the surface 20 a of the resin layer 20 . Moreover, it is preferable that the protective layer 22 has an oxygen blocking property. Oxidation of the conductor 14 can be suppressed by having an oxygen blocking property. When the conductor 14 protrudes, the protruding portions 14a and 14b of the conductor 14 are likely to be oxidized, so it is particularly effective for the protective layer 22 to have an oxygen blocking property. It is more preferable that the protective layer 22 has the ability to block gases of elements other than oxygen, in addition to blocking oxygen.
  • the protective layer 22 and the resin layer 20 are in direct contact with each other, there is no separate layer between the protective layer 22 and the resin layer 20, and the protective layer 22 is formed on the surface 20a of the resin layer 20. That's what I mean.
  • the protective layer 22 and the resin layer 20 are in direct contact with each other, and another layer may be provided between the protective layer 22 and the resin layer 20 .
  • an intermediate layer (not shown) that facilitates removal of the protective layer 22 may be provided between the protective layer 22 and the resin layer 20 .
  • the intermediate layer contains, for example, fluororesin.
  • the fluororesin is, for example, a fluoroethylene vinyl ether alternating copolymer. More specifically, the fluororesin is Lumiflon (registered trademark) LF200 (trade name, manufactured by AGC Corporation).
  • the intermediate layer made of the above-described fluororesin, adhesion of cutting debris to the surface 20a of the resin layer 20 after the protective layer 22 is removed is suppressed.
  • the resin layer 20, the intermediate layer (not shown) and the protective layer 22 are collectively referred to as a coating layer.
  • the structure of the resin layer 20 and the protective layer 22 without an intermediate layer is also called a coating layer.
  • the structure 10 has anisotropic conductivity, and although it has conductivity in the thickness direction Dt, its conductivity in the direction parallel to the surface 12a of the insulating film 12 is sufficiently low.
  • the structure 10 has, for example, a rectangular outer shape, as shown in FIG.
  • the outer shape of the structure 10 is not limited to a rectangle, and may be, for example, a circle.
  • the outer shape of the structure 10 can be shaped according to the application, ease of production, and the like.
  • the conductor 14 protrudes from both surfaces of the insulating film 12 in the thickness direction Dt, but may protrude from at least one surface of the insulating film 12 in the thickness direction Dt. When the conductor 14 protrudes from at least one surface in the thickness direction Dt of the insulating film 12, it is preferable that the conductor protrudes from the front surface 12a or the back surface 12b in the configuration in which the conductor 14 projects from one surface.
  • the protective layer 22 prevents the structure 10 from being separated into individual pieces by cutting such as dicing. Even if chips generated from the body 10 adhere to the protective layer 22 , they do not adhere to the resin layer 20 . Therefore, by removing the protective layer 22 after singulation, it is possible to obtain the resin layer 20 to which cutting chips and the like are not attached. The influence of cutting debris can be suppressed by removing the cutting debris adhering when the structure 10 is singulated by removing the protective layer 22, for example. As a result, the singulated structure 10 can be inserted and joined, for example, between a semiconductor element, an electronic component, and a circuit board without physical obstacles.
  • FIGS. 3 to 5 are schematic cross-sectional views showing an example of cutting the structure according to the embodiment of the present invention in order of steps. 3 to 5, the same components as those of the structure 10 shown in FIG. 1 are denoted by the same reference numerals, and detailed description thereof will be omitted.
  • a protective layer 22 is provided on one surface of the two resin layers 20, ie, on the surface 12a of the insulating film 12.
  • a support 37 is attached to the resin layer 20 on the back surface 12b side of the insulating film 12 of the structure 10 using a thermal release layer 36 . By attaching the support 37, the individualization of the structure 10 and the like can be easily carried out.
  • a dicing tape 38 is provided on the opposite side of the support 37 from the thermal release layer 36 .
  • the configuration of the thermal release layer 36 is not particularly limited as long as it can bond the structure 10 and the support 37 described above. ), or double-sided type Rivaalpha (registered trademark) manufactured by Nitto Denko Corporation.
  • the support 37 preferably has the same outer shape as the above-described laminated structure so that the laminated structure can be easily handled in the above-described substrate removal step.
  • a silicon substrate for example, is used for the support 37 .
  • the support 37 is not limited to a silicon substrate.
  • ceramic substrates such as SiC, SiN, GaN, and alumina (Al 2 O 3 ) substrates, glass substrates, fiber-reinforced plastic substrates, and metal substrates can be used. can.
  • Fiber-reinforced plastic substrates include FR-4 (Flame Retardant Type 4) substrates, which are printed wiring substrates.
  • a dicing tape 38 fixes the support 37 .
  • the dicing tape 38 is not particularly limited, and known tapes can be used as appropriate.
  • the structure 10 having the configuration shown in FIG. 3 is cut from the surface 22a side of the protective layer 22 on the resin layer 20 on the surface 12a side of the insulating film 12 as shown in FIG. At this time, shavings 39 are generated, and the shavings 39 adhere to the surface 22 a of the protective layer 22 .
  • the surface 22 a of the protective layer 22 is the surface opposite to the insulating film 12 and is the outermost surface of the structure 10 .
  • the protective layer 22 is removed as shown in FIG. By removing the protective layer 22, the resin layer 20 with no chips 39 attached to the surface 20a appears. Thereby, in the structure 10, the influence of the cutting waste 39 can be suppressed.
  • removal of the protective layer 22 can be appropriately performed according to the composition, physical properties, or the like of the protective layer 22 .
  • the protective layer 22 is made of PVA (polyvinyl alcohol)
  • hot water for example, is used as a solvent for the removing liquid to dissolve the protective layer 22 .
  • Hot water is water with a temperature of 35° C. or higher.
  • the anisotropically conductive member 11 is obtained by the protective layer removing step of removing the protective layer 22 of the structure 10 described above.
  • the anisotropically conductive member 11 is a structure in which the protective layer 22 is not provided in the structure 10 .
  • the insulating film 12 electrically insulates the plurality of conductors 14 made of conductors from each other.
  • the insulating film has electrical insulation.
  • Insulating film 12 also has a plurality of pores 13 in which conductors 14 are formed.
  • the insulating film is made of, for example, an inorganic material.
  • an inorganic material for the insulating film, one having an electrical resistivity of, for example, about 10 14 ⁇ cm can be used.
  • "made of inorganic material” is a rule for distinguishing from polymer materials, and is not a rule limited to insulating substrates composed only of inorganic materials, but inorganic materials as the main component (50% by mass above).
  • the insulating film is composed of, for example, an anodized film, as described above.
  • the insulating film can also be made of, for example, metal oxides, metal nitrides, glass, ceramics such as silicon carbide and silicon nitride, carbon base materials such as diamond-like carbon, polyimide, composite materials thereof, and the like.
  • the insulating film may be, for example, a film formed of an inorganic material containing 50% by mass or more of a ceramic material or a carbon material on an organic material having through holes.
  • the length of the insulating film 12 in the thickness direction Dt is preferably in the range of 1 to 1000 ⁇ m, more preferably in the range of 5 to 500 ⁇ m, and more preferably in the range of 10 to 300 ⁇ m. More preferably within. When the thickness of the insulating film 12 is within this range, the handleability of the insulating film 12 is improved.
  • the thickness ht of the insulating film 12 is preferably 30 ⁇ m or less, more preferably 5 to 20 ⁇ m, from the viewpoint of ease of winding.
  • the thickness of the anodized film is determined by cutting the anodized film in the thickness direction Dt using a focused ion beam (FIB), and observing the cross section with a field emission scanning electron microscope (FE-SEM). This is a value calculated as an average value obtained by photographing the surface (magnification of 50,000 times) using , and measuring 10 points.
  • the distance between the conductors 14 in the insulating film 12 is preferably 5 nm to 800 nm, more preferably 10 nm to 200 nm, even more preferably 20 nm to 60 nm.
  • the insulating film 12 sufficiently functions as an electrically insulating partition between the conductors 14 .
  • the interval between each conductor means the width between adjacent conductors. Mean value measured at points.
  • the average diameter of the pores is preferably 1 ⁇ m or less, more preferably 5 to 500 nm, still more preferably 20 to 400 nm, even more preferably 40 to 200 nm, and 50 to 100 nm. Most preferably there is.
  • the conductor 14 having the above average diameter can be obtained.
  • the average diameter of the pores 13 is obtained by photographing the surface of the insulating film 12 from directly above with a scanning electron microscope at a magnification of 100 to 10000 times.
  • the diameters of the pores are measured and used as opening diameters, and the average value of these opening diameters is calculated as the average diameter of the pores.
  • the magnification can be appropriately selected within the range described above so that a photographed image from which 20 or more pores can be extracted can be obtained.
  • the aperture diameter measures the maximum distance between the ends of the pore portions. That is, since the shape of the opening of the pore is not limited to a substantially circular shape, when the shape of the opening is non-circular, the maximum distance between the ends of the pore portion is taken as the opening diameter. Therefore, for example, even in the case of a pore having a shape in which two or more pores are integrated, this is regarded as one pore, and the maximum value of the distance between the ends of the pore portion is taken as the opening diameter. .
  • the plurality of conductors 14 are provided electrically insulated from each other in the insulating film 12, for example, the anodized film 15, as described above.
  • the plurality of conductors 14 have electrical conductivity.
  • the conductor is composed of an electrically conductive material.
  • the conductive substance is not particularly limited, and includes metals. Preferred examples of metals include gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), and nickel (Ni). From the viewpoint of electrical conductivity, copper, gold, aluminum and nickel are preferred, copper and gold are more preferred, and copper is most preferred.
  • oxide conductive materials can be mentioned. Examples of conductive oxide materials include indium-doped tin oxide (ITO).
  • the conductor can also be made of a conductive resin containing nanoparticles such as Cu or Ag, for example.
  • the height H of the conductor 14 in the thickness direction Dt is preferably 10-300 ⁇ m, more preferably 20-30 ⁇ m.
  • the average diameter d of the conductors 14 is preferably 1 ⁇ m or less, more preferably 5 to 500 nm, even more preferably 20 to 400 nm, even more preferably 40 to 200 nm, even more preferably 50 to 100 nm. is most preferred.
  • the density of the conductors 14 is preferably 20,000/mm 2 or more, more preferably 2,000,000/mm 2 or more, even more preferably 10,000,000/mm 2 or more, and 50,000,000. /mm 2 or more is particularly preferable, and 100 million/mm 2 or more is most preferable.
  • the center-to-center distance p between adjacent conductors 14 is preferably 20 nm to 500 nm, more preferably 40 nm to 200 nm, even more preferably 50 nm to 140 nm.
  • the average diameter of the conductor is obtained by photographing the surface of the anodized film from directly above with a scanning electron microscope at a magnification of 100 to 10000 times. In the photographed image, at least 20 conductors whose circumferences are continuous in a ring are extracted, the diameters of the conductors are measured, and the average value of these opening diameters is calculated as the average diameter of the conductors.
  • the magnification can be appropriately selected within the range described above so that a photographed image from which 20 or more conductors can be extracted can be obtained.
  • the aperture diameter measures the maximum distance between the ends of the conductor portions. That is, since the shape of the opening of the conductor is not limited to a substantially circular shape, when the shape of the opening is non-circular, the maximum value of the distance between the ends of the conductor portion is taken as the opening diameter. Therefore, for example, even in the case of a conductor having a shape in which two or more conductors are integrated, this is regarded as one conductor, and the maximum value of the distance between the ends of the conductor portions is taken as the opening diameter.
  • the protrusion is part of the conductor and has a columnar shape.
  • the projecting portion preferably has a columnar shape because it can increase the contact area with the object to be welded.
  • the average protrusion length ha of the protrusions 14a and the average length hb of the protrusions 14b are preferably 30 nm to 500 nm, and more preferably 100 nm or less as the upper limit.
  • the average protrusion length ha of the protrusions 14a and the average length hb of the protrusions 14b are obtained by obtaining cross-sectional images of the protrusions using a field emission scanning electron microscope as described above, and based on the cross-sectional images. is the average value obtained by measuring the height of each at 10 points.
  • the resin layer covers at least one of the front and back surfaces of the insulating film as described above, and protects the insulating film and the conductor. For example, if the conductor has a projecting portion, the resin layer embeds the projecting portion. That is, the resin layer covers the end of the conductor protruding from the insulating film and protects the protruding portion.
  • the resin layer preferably exhibits fluidity in a temperature range of, for example, 50° C. to 200° C. and hardens at 200° C. or higher in order to exhibit the above functions.
  • the resin layer is, for example, a thermoplastic layer made of a thermoplastic resin or the like, and the resin layer will be described later in detail.
  • the average protrusion lengths ha and hb of the conductors 14 are preferably less than the average thickness hm of the resin layer 20 . If both the average protrusion length ha of the protrusions 14a of the conductor 14 and the average length hb of the protrusions 14b of the conductor 14 are less than the average thickness hm of the resin layer 20, the protrusions 14a and 14b , and the conductor 14 is protected by the resin layer 20 .
  • the average thickness hm of the resin layer 20 is the average distance from the front surface 12 a of the insulating film 12 or the average distance from the back surface 12 b of the insulating film 12 .
  • the average thickness hm of the resin layer 20 described above is obtained by cutting the resin layer in the thickness direction Dt of the structure 10 and observing the cut cross section using a field emission scanning electron microscope (FE-SEM). The distance from the surface 12a of the insulating film 12 is measured at 10 points corresponding to , and the average value of the measured values at the 10 points. Also, the distance from the back surface 12b of the insulating film 12 was measured at 10 points corresponding to the resin layer, and the average value of the measured values at 10 points was obtained.
  • the average thickness hm of the resin layer is preferably 200-1000 nm, more preferably 400-600 nm. If the resin layer has an average thickness of 200 to 1000 nm as described above, the effect of protecting the projecting portion of the conductor 14 can be sufficiently exhibited.
  • the protective layer 22 protects the resin layer 20 as described above, and the protective layer 22 prevents chips 39 and the like from adhering to the surface 20 a of the resin layer 20 .
  • the protective layer 22 is composed of an organic material as described above. Also, the protective layer 22 is the outermost layer of the structure 10 .
  • the protective layer 22 preferably has oxygen barrier properties as described above. Oxidation of the conductor 14 can be suppressed by having an oxygen blocking property. When the conductor 14 protrudes from the insulating film 12, the protrusions 14a and 14b of the conductor 14 are exposed and easily oxidized. That the protective layer 22 has an oxygen blocking property means that the oxygen permeability coefficient is 1.5 ⁇ 10 17 m 3 (STP) m ⁇ m ⁇ 2 ⁇ s ⁇ 1 ⁇ kPa ⁇ 1 or less. STP (standard temperature and pressure) indicates the temperature and pressure in the standard state. STP is an absolute temperature of 273.15 K (Kelvin) and a pressure of 1.01325 ⁇ 10 5 Pa, ie, 0° C. and 1 atmosphere.
  • STP standard temperature and pressure
  • the protective layer 22 preferably has an oxygen permeability coefficient of 1.5 ⁇ 10 16 m 3 (STP) m ⁇ m ⁇ 2 ⁇ s ⁇ 1 ⁇ kPa ⁇ 1 or less, more preferably 7.0 ⁇ 10 15 m 3 (STP) m ⁇ m ⁇ 2 ⁇ s ⁇ 1 ⁇ kPa ⁇ 1 or less.
  • the lower limit of the oxygen permeability coefficient is 3 ⁇ 10 15 m 3 (STP) m ⁇ m ⁇ 2 ⁇ s ⁇ 1 ⁇ kPa ⁇ 1 .
  • the oxygen permeability coefficient is a value measured using a differential pressure method.
  • a protective layer film with a diameter of 50 mm is used for measuring the oxygen permeability.
  • the protective layer is a laminate film
  • the laminate film is cut into a piece having a diameter of 50 mm and used for measuring the oxygen permeability coefficient. The thickness is actually measured.
  • the protective layer 22 is composed of an organic material, and the organic material is, for example, resin.
  • the protective layer 22 is made of, for example, PVA (polyvinyl alcohol) or PVDC (polyvinylidene chloride).
  • PVA may be a copolymer EVOH (ethylene vinyl alcohol copolymer) with ethylene.
  • Polyacrylonitrile can also be used.
  • PVDC may be a copolymer with acrylonitrile or vinyl chloride. Examples of commercial products include Saran Resin (trade name, PDVC type) manufactured by Asahi Kasei Corporation and Maxieve (trade name, epoxy type) manufactured by Mitsubishi Gas Chemical Company, Inc.
  • the protective layer 22 may be formed of epoxy resin.
  • PVDC-coated film for example, a PVDC-coated film is used.
  • V Barrier registered trademark, manufactured by Mitsui Chemicals Tohcello Co., Ltd.
  • Bonyl-K manufactured by Kohjin Film & Chemicals Co., Ltd.
  • the protective layer 22 preferably has an adhesiveness of 2 to 10 N/25 mm to other layers in contact with it.
  • 2 to 10 N / 25 mm which represents the above-mentioned adhesiveness, is a value obtained by a method according to JIS (Japanese Industrial Standards) K 6854-2 "Adhesive-Peeling adhesive strength test method-Part 2: 180 degree peeling" is.
  • the protective layer 22 has an adhesiveness of 2 to 10 N/25 mm to other layers in contact with it, the function of the protective layer 22 can be maintained and the protective layer 22 can be easily removed.
  • Examples of the protective layer having an adhesiveness of 2 to 10 N/25 mm are PVA and PVDC.
  • the other layer in contact means the layer immediately below the protective layer 22 in contact, and in FIG. 1, the resin layer 20 is the other layer in contact. If another layer, for example, an intermediate layer to be described later, is formed between the protective layer 22 and the resin layer 20, and the intermediate layer is in contact with the protective layer 22, the other layer in contact with the intermediate layer become.
  • adhesiveness for example, when the protective layer 22 is made of saran resin, a small amount of isocyanate-based adhesive can be added to control adhesiveness.
  • the protective layer 22 is subjected to dissolution removal with a remover.
  • the removal liquid contains a solvent having a dissolution rate of 1 ⁇ m/s or more for the protective layer 22 at a temperature of 25°C.
  • the dissolution rate of the protective layer 22 can be measured by known means. For example, it is possible to measure the dissolution rate of the protective layer 22 using a device such as RDA-760 manufactured by Litho Tech Japan.
  • the protective layer 22 can be easily removed by a removing liquid having a dissolution rate of the protective layer 22 of 1 ⁇ m/s or more.
  • the removal liquid may contain multiple types of solvents, and the solvent may be an organic solvent.
  • the removing liquid preferably contains ethyl acetate.
  • the solvent contained in the removing liquid is, for example, methyl ethyl ketone (MEK) or hot water.
  • the removing liquid may be a mixed solution of tetrahydrofuran (THF) and toluene (TOL).
  • the average thickness hj of the protective layer is preferably 200-1000 nm, more preferably 400-600 nm. If the average thickness of the protective layer is 200 to 1000 nm as described above, adhesion of cutting debris 39 to the resin layer 20 can be suppressed.
  • the average thickness hj of the protective layer 22 is the average distance from the surface 20 a of the resin layer 20 .
  • the average thickness hj of the protective layer 22 described above is obtained by cutting the protective layer in the thickness direction Dt of the structure 10 and observing the cut section using a field emission scanning electron microscope (FE-SEM). The distance from the surface 20a of the resin layer 20 is measured at 10 points corresponding to , and the average value of the measured values at 10 points.
  • the protective layer 22 is removed when chips generated from the structural body 10 adhere to the protective layer 22 when the structural body 10 is singulated by cutting such as dicing.
  • the protective layer 22 can be removed by, for example, dissolution or peeling. As a result, the influence of cutting debris can be suppressed, and the singulated structure 10 can be inserted between, for example, a semiconductor element, an electronic component, and a circuit board without physical obstacles. can be spliced.
  • the protective layer 22 is made of a water-soluble organic material, for example, the protective layer 22 is removed with warm water after dicing, thereby removing shavings together with the protective layer 22 .
  • the composition for forming a protective layer forms a protective layer composed of an organic substance and contains a resin.
  • the resin is, for example, an epoxy resin.
  • the protective layer-forming composition may also be, for example, PVA (polyvinyl alcohol) or PVDC (polyvinylidene chloride).
  • the composition for forming the protective layer is the specific example constituting the protective layer 22 described above.
  • the structure 10 is cut in the thickness direction Dt, and the cross-sectional observation of the cut section is performed using a field emission scanning electron microscope (FE-SEM). It is the average value obtained by measuring 10 points corresponding to each size.
  • FE-SEM field emission scanning electron microscope
  • FIGS. 1 and 2 are schematic cross-sectional views showing an example of the method for manufacturing the structure according to the embodiment of the present invention in order of steps. 6 to 12, the same components as those shown in FIGS. 1 and 2 are denoted by the same reference numerals, and detailed description thereof will be omitted.
  • the structure 10 shown in FIG. An aluminum substrate is used to form an aluminum anodized film. Therefore, in one example of the structure manufacturing method, first, as shown in FIG. 6, an aluminum substrate 30 is prepared. The size and thickness of the aluminum substrate 30 are appropriately determined according to the thickness of the insulating film 12 of the finally obtained structure 10 (see FIG. 1), the processing equipment, and the like.
  • the aluminum substrate 30 is, for example, a rectangular plate. Note that the substrate is not limited to the aluminum substrate, and a metal substrate on which an electrically insulating insulating film 12 can be formed can be used.
  • one surface 30a (see FIG. 6) of the aluminum substrate 30 is anodized.
  • one surface 30a (see FIG. 6) of the aluminum substrate 30 is anodized, and as shown in FIG. That is, an anodized film 15 is formed.
  • a barrier layer 31 is present at the bottom of each pore 13 .
  • the above-described anodizing process is called an anodizing process.
  • Insulating film 12 having a plurality of pores 13 has barrier layer 31 at the bottom of each of pores 13 as described above, but barrier layer 31 shown in FIG. 7 is removed. As a result, the insulating film 12 (see FIG. 8) without the barrier layer 31 and having the plurality of pores 13 is obtained.
  • the process of removing the barrier layer 31 described above is called a barrier layer removing process.
  • the barrier layer removing step the barrier layer 31 of the insulating film 12 is removed and at the same time the bottom 32c (see FIG. 8) of the pore 13 is removed by using an alkaline aqueous solution containing ions of the metal M1 having a hydrogen overvoltage higher than that of aluminum.
  • a metal layer 35a (see FIG. 8) made of a metal (metal M1) is formed on the surface 32d (see FIG. 8). As a result, the aluminum substrate 30 exposed in the pores 13 is covered with the metal layer 35a.
  • the alkaline aqueous solution containing ions of the metal M1 described above may further contain an aluminum ion-containing compound (sodium aluminate, aluminum hydroxide, aluminum oxide, etc.).
  • the content of the aluminum ion-containing compound is preferably 0.1 to 20 g/L, more preferably 0.3 to 12 g/L, and even more preferably 0.5 to 6 g/L in terms of the amount of aluminum ions.
  • plating is performed from the surface 12a of the insulating film 12 having a plurality of pores 13 extending in the thickness direction Dt.
  • the metal layer 35a can be used as an electrode for electrolytic plating.
  • a metal 35b is used for plating, and plating progresses from the metal layer 35a formed on the surface 32d (see FIG. 8) of the bottom 32c (see FIG. 8) of the pore 13 as a starting point.
  • the inside of the pores 13 of the insulating film 12 is filled with the metal 35b forming the conductor 14.
  • the conductive conductors 14 are formed.
  • the metal layer 35a and the metal 35b are collectively referred to as the filled metal 35.
  • the process of filling the pores 13 of the insulating film 12 with the metal 35b is called a metal filling process.
  • the conductor 14 is not limited to being made of metal, but any conductive material can be used. Electroplating is used for the metal filling process, and the metal filling process will be described later in detail. Note that the surface 12 a of the insulating film 12 corresponds to one surface of the insulating film 12 . After the metal filling process, as shown in FIG.
  • the surface 12a of the insulating film 12 on the side where the aluminum substrate 30 is not provided is partially removed in the thickness direction Dt after the metal filling process, and filled in the metal filling process.
  • the metal 35 is made to protrude from the surface 12 a of the insulating film 12 . That is, the conductor 14 is made to protrude from the surface 12 a of the insulating film 12 . Thereby, the projecting portion 14a is obtained.
  • a process of projecting the conductor 14 from the surface 12a of the insulating film 12 is called a surface metal projecting process.
  • the aluminum substrate 30 is removed as shown in FIG. The process of removing the aluminum substrate 30 is called a substrate removing process.
  • the surface of the insulating film 12 on which the aluminum substrate 30 was provided that is, the back surface 12b is partially removed in the thickness direction Dt, and filled in the metal filling step.
  • the metal 35 that is, the conductor 14 is made to protrude from the back surface 12 b of the insulating film 12 .
  • the projecting portion 14b is obtained.
  • the above-described front surface metal protruding step and rear surface metal protruding step may include both steps, or may include one of the front surface metal protruding step and the rear surface metal protruding step.
  • the front metal protruding process and the back metal protruding process correspond to the "protruding process", and both the front metal protruding process and the back metal protruding process are protruding processes.
  • conductors 14 protrude from a front surface 12a and a rear surface 12b of the insulating film 12, respectively, and have projecting portions 14a and 14b.
  • a resin layer 20 (see FIG. 1) is formed to cover the entire surface 12a and the entire back surface 12b of the insulating film 12 from which the conductors 14 protrude.
  • a process for forming the resin layer 20 will be described later.
  • a protective layer 22 (see FIG. 1) is formed on the surface 20a of the resin layer 20 (see FIG. 1).
  • a process for forming the protective layer 22 will be described later.
  • the structure 10 shown in FIG. 1 can be obtained.
  • a resin layer 20 (see FIG. 1) covering the entire surface 12a and the entire back surface 12b of the insulating film 12 is formed in the state shown in FIG.
  • the structure 10 is obtained by forming the protective layer 22 (see FIG. 1) on the surface 20a of the resin layer 20 (see FIG. 1).
  • the barrier layer removing step described above the barrier layer is removed using an alkaline aqueous solution containing ions of the metal M1 having a hydrogen overvoltage higher than that of aluminum.
  • a metal layer 35a of the metal M1 which is less likely to generate hydrogen gas than aluminum, is formed.
  • the in-plane uniformity of metal filling is improved. It is considered that this is because generation of hydrogen gas by the plating solution is suppressed, and metal filling by electrolytic plating is facilitated.
  • a holding step in which a voltage (holding voltage) selected from a range of less than 30% of the voltage in the anodizing step is held at a voltage of 95% or more and 105% or less for a total of 5 minutes or more, It has been found that, in combination with the application of an alkaline aqueous solution containing ions of metal M1, the uniformity of metal filling during plating is greatly improved. Therefore, it is preferable that there is a holding step.
  • a layer of metal M1 is formed under the barrier layer by using an alkaline aqueous solution containing ions of metal M1, which damages the interface between the aluminum substrate and the anodized film. This is considered to be due to the fact that the dissolution of the barrier layer can be suppressed and the dissolution uniformity of the barrier layer is improved.
  • the metal layer 35a made of metal (metal M1) was formed on the bottom of the pores 13, but the present invention is not limited to this.
  • An aluminum substrate 30 is exposed on the bottom.
  • the aluminum substrate 30 may be used as an electrode for electroplating while the aluminum substrate 30 is exposed.
  • anodized film for example, an anodized aluminum film is used because pores having a desired average diameter are formed and conductors are easily formed, as described above.
  • a valve metal is used for the metal substrate.
  • specific examples of valve metals include aluminum as described above, and tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, antimony, and the like.
  • the anodized film of aluminum is preferable because it has good dimensional stability and is relatively inexpensive. Therefore, it is preferable to manufacture the structure using an aluminum substrate.
  • the thickness of the anodized film is the same as the thickness ht (see FIG. 2) of the insulating film 12 described above.
  • a metal substrate is used for manufacturing a structure, and is a substrate for forming an anodized film.
  • a metal substrate on which an anodized film can be formed is used as described above, and a substrate composed of the valve metal described above can be used.
  • an aluminum substrate is used as the metal substrate because, as described above, an anodized film can be easily formed as an insulating film.
  • the aluminum substrate used to form the insulating film 12 is not particularly limited, and specific examples thereof include a pure aluminum plate; an alloy plate containing aluminum as a main component and a trace amount of foreign elements; low-purity aluminum (for example, Recycled materials) substrates on which high-purity aluminum is vapor-deposited; substrates in which high-purity aluminum is coated on the surface of silicon wafers, quartz, glass, etc. by vapor deposition, sputtering, etc.; resin substrates laminated with aluminum; .
  • one surface on which an anodized film is formed by anodizing treatment preferably has an aluminum purity of 99.5% by mass or more, more preferably 99.9% by mass or more, and 99% by mass. More preferably, it is at least 0.99% by mass. When the aluminum purity is within the above range, the regularity of the micropore arrangement is sufficient.
  • the aluminum substrate is not particularly limited as long as it can form an anodized film, and for example, JIS (Japanese Industrial Standards) 1050 material is used.
  • one surface of the aluminum substrate to be anodized is previously subjected to heat treatment, degreasing treatment and mirror finish treatment.
  • the heat treatment, the degreasing treatment and the mirror finish treatment can be performed in the same manner as the treatments described in paragraphs [0044] to [0054] of JP-A-2008-270158.
  • the mirror finish treatment before the anodizing treatment is, for example, electropolishing, and for electropolishing, for example, an electropolishing liquid containing phosphoric acid is used.
  • a conventionally known method can be used for the anodizing treatment, but from the viewpoint of increasing the regularity of the micropore array and ensuring the anisotropic conductivity of the structure, it is recommended to use a self-ordering method or a constant voltage treatment. is preferred.
  • the same treatments as those described in paragraphs [0056] to [0108] and [Fig. can apply.
  • the method of manufacturing the structure may have a holding step.
  • a voltage of 95% or more and 105% or less of the holding voltage selected from the range of 1 V or more and less than 30% of the voltage in the above-mentioned anodizing treatment step is applied for a total of 5 minutes or more
  • the total voltage is 95% or more and 105% or less of the holding voltage selected from the range of 1 V or more and less than 30% of the voltage in the above-mentioned anodizing treatment step.
  • This is a step of applying electrolytic treatment for 5 minutes or more.
  • the "voltage in the anodizing process” is the voltage applied between the aluminum and the counter electrode. mean value.
  • the voltage in the holding step should be 5% or more and 25% or less of the voltage in the anodization treatment. It is preferably 5% or more and 20% or less.
  • the total holding time in the holding step is preferably 5 minutes or more and 20 minutes or less, more preferably 5 minutes or more and 15 minutes or less, and 5 minutes or more. It is more preferably 10 minutes or less.
  • the holding time in the holding step may be 5 minutes or more in total, but preferably 5 minutes or more continuously.
  • the voltage in the holding step may be set by dropping continuously or stepwise from the voltage in the anodizing step to the voltage in the holding step. It is preferable to set the voltage to 95% or more and 105% or less of the holding voltage within 1 second after the process is finished.
  • the above-described holding step can also be performed continuously with the above-described anodizing step, for example by lowering the electrolytic potential at the end of the above-described anodizing step.
  • the electrolytic solution and treatment conditions similar to those of the above-described conventionally known anodizing treatment can be employed, except for the electrolytic potential.
  • a barrier layer (not shown) exists at the bottom of the micropores as described above.
  • a barrier layer removing step is provided to remove this barrier layer.
  • the barrier layer removing step is, for example, a step of removing the barrier layer of the anodized film using an alkaline aqueous solution containing ions of metal M1 having a hydrogen overvoltage higher than that of aluminum.
  • the barrier layer removing step described above the barrier layer is removed and a conductive layer made of metal M1 is formed on the bottom of the micropores.
  • the hydrogen overvoltage refers to the voltage required to generate hydrogen.
  • the hydrogen overvoltage of aluminum (Al) is ⁇ 1.66 V (Journal of the Chemical Society of Japan, 1982, (8) , p 1305-1313).
  • Metal M1 having a hydrogen overvoltage higher than that of aluminum and its hydrogen overvoltage value are shown below.
  • ⁇ Metal M1 and hydrogen ( 1N H2SO4 ) overvoltage> ⁇ Platinum (Pt): 0.00V Gold (Au): 0.02V ⁇ Silver (Ag): 0.08V ⁇ Nickel (Ni): 0.21V ⁇ Copper (Cu): 0.23V - Tin (Sn): 0.53V ⁇ Zinc (Zn): 0.70V
  • the pores 13 can also be formed by enlarging the micropores and removing the barrier layer.
  • pore widening treatment is used to expand the diameter of the micropores.
  • the pore widening treatment is a treatment in which the anodized film is immersed in an acid aqueous solution or an alkaline aqueous solution to dissolve the anodized film and expand the pore diameter of the micropores.
  • Aqueous solutions of inorganic acids such as hydrochloric acid or mixtures thereof, or aqueous solutions of sodium hydroxide, potassium hydroxide and lithium hydroxide can be used.
  • the pore-widening treatment can also remove the barrier layer at the bottom of the micropores, and by using an aqueous sodium hydroxide solution in the pore-widening treatment, the micropores are enlarged and the barrier layer is removed.
  • the metal filled as a conductor inside the pores 13 and the metal constituting the metal layer are materials having an electrical resistivity of 10 3 ⁇ cm or less.
  • the metals mentioned above include gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), and zinc (Zn).
  • the conductor copper (Cu), gold (Au), aluminum (Al), and nickel (Ni) are preferable from the viewpoint of electrical conductivity and formation by plating. ) is more preferred, and copper (Cu) is even more preferred.
  • Electroplating or electroless plating can be used as the plating method for filling the inside of the pores with metal.
  • the pause time should be 10 seconds or longer, preferably 30 to 60 seconds. It is also desirable to apply ultrasonic waves to promote agitation of the electrolyte.
  • the electrolysis voltage is usually 20 V or less, preferably 10 V or less, but it is preferable to measure the deposition potential of the target metal in the electrolyte to be used in advance and perform constant potential electrolysis within +1 V of the potential.
  • constant potential electrolysis it is desirable to use cyclic voltammetry together, and a potentiostat device such as Solartron, BAS, Hokuto Denko, and IVIUM can be used.
  • plating solution A conventionally known plating solution can be used as the plating solution. Specifically, when copper is deposited, an aqueous solution of copper sulfate is generally used, and the concentration of copper sulfate is preferably 1 to 300 g/L, more preferably 100 to 200 g/L. preferable. In addition, the addition of hydrochloric acid to the electrolytic solution can promote the deposition. In this case, the hydrochloric acid concentration is preferably 10-20 g/L. When depositing gold, it is desirable to use a sulfuric acid solution of tetrachlorogold and perform plating by alternating current electrolysis.
  • the plating solution preferably contains a surfactant.
  • a known surfactant can be used.
  • Sodium lauryl sulfate which is conventionally known as a surfactant added to plating solutions, can also be used as it is.
  • Both ionic (cationic, anionic, amphoteric) and nonionic (nonionic) hydrophilic parts can be used.
  • a cationic ray activator is desirable. It is desirable that the concentration of the surfactant in the composition of the plating solution is 1% by mass or less. In the electroless plating method, it takes a long time to completely fill the metal into the pores composed of high aspect ratio pores. Therefore, it is desirable to fill the pores with the metal using the electroplating method.
  • the substrate removal step is a step of removing the aluminum substrate described above after the metal filling step.
  • a method for removing the aluminum substrate is not particularly limited, and a suitable method includes, for example, a method of removing by dissolution.
  • a treatment liquid that does not easily dissolve the anodized film but easily dissolves aluminum.
  • a treatment liquid preferably has a dissolution rate for aluminum of 1 ⁇ m/minute or more, more preferably 3 ⁇ m/minute or more, and even more preferably 5 ⁇ m/minute or more.
  • the dissolution rate in the anodized film is preferably 0.1 nm/min or less, more preferably 0.05 nm/min or less, and even more preferably 0.01 nm/min or less.
  • the treatment liquid preferably contains at least one metal compound with a lower ionization tendency than aluminum and has a pH (hydrogen ion exponent) of 4 or less or 8 or more, and the pH is 3 or less or It is more preferably 9 or more, and even more preferably 2 or less or 10 or more.
  • a pH hydrogen ion exponent
  • the processing liquid for dissolving aluminum is based on an acid or alkaline aqueous solution, and includes, for example, manganese, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead, antimony, bismuth, copper, mercury, silver, palladium, and platinum. , gold compounds (eg, chloroplatinic acid), their fluorides, their chlorides, and the like. Among them, an acid aqueous solution base is preferred, and a chloride blend is preferred.
  • a treatment solution obtained by blending mercury chloride with an aqueous hydrochloric acid solution (hydrochloric acid/mercury chloride) and a treatment solution obtained by blending an aqueous hydrochloric acid solution with copper chloride (hydrochloric acid/copper chloride) are preferable from the viewpoint of treatment latitude.
  • the composition of the treatment liquid for dissolving aluminum is not particularly limited, and for example, a bromine/methanol mixture, a bromine/ethanol mixture, aqua regia, or the like can be used.
  • the acid or alkali concentration of the treatment liquid for dissolving aluminum is preferably 0.01 to 10 mol/L, more preferably 0.05 to 5 mol/L. Furthermore, the treatment temperature using the treatment liquid for dissolving aluminum is preferably -10°C to 80°C, more preferably 0°C to 60°C.
  • the above-described dissolution of the aluminum substrate is performed by bringing the aluminum substrate after the above-described plating process into contact with the above-described treatment liquid.
  • the contacting method is not particularly limited, and includes, for example, an immersion method and a spray method. Among them, the immersion method is preferable.
  • the contact time at this time is preferably 10 seconds to 5 hours, more preferably 1 minute to 3 hours.
  • the insulating film 12 may be provided with a support, for example.
  • the support preferably has the same outer shape as the insulating film 12 . By attaching the support, the handleability is increased.
  • an acid aqueous solution or an alkaline aqueous solution that dissolves the insulating film 12 that is, aluminum oxide (Al 2 O 3 ) without dissolving the metal that constitutes the conductor 14 is used.
  • the insulating film 12 having the metal-filled pores 13 is brought into contact with the acid aqueous solution or alkaline aqueous solution described above, thereby partially removing the insulating film 12 .
  • the method of bringing the above acid aqueous solution or alkaline aqueous solution into contact with the insulating film 12 is not particularly limited, and examples thereof include an immersion method and a spray method. Among them, the immersion method is preferred.
  • an aqueous solution When using an acid aqueous solution, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid and hydrochloric acid, or a mixture thereof. Among them, an aqueous solution containing no chromic acid is preferable because of its excellent safety.
  • the concentration of the acid aqueous solution is preferably 1-10 mass %.
  • the temperature of the acid aqueous solution is preferably 25-60°C.
  • an aqueous alkali solution it is preferable to use an aqueous solution of at least one alkali selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the concentration of the alkaline aqueous solution is preferably 0.1 to 5% by mass.
  • the temperature of the alkaline aqueous solution is preferably 20 to 35°C. Specifically, for example, a 50 g/L, 40° C. phosphoric acid aqueous solution, a 0.5 g/L, 30° C. sodium hydroxide aqueous solution, or a 0.5 g/L, 30° C. potassium hydroxide aqueous solution is preferably used. .
  • the immersion time in the acid aqueous solution or alkaline aqueous solution is preferably 8 to 120 minutes, more preferably 10 to 90 minutes, even more preferably 15 to 60 minutes.
  • the immersion time refers to the sum of each immersion time when short-time immersion treatments are repeated.
  • the metal 35 that is, the conductor 14 is projected from the front surface 12a or the back surface 12b of the insulating film 12.
  • the upper limit is more preferably 100 nm or less. That is, the protrusion amount of the protrusion 14a from the front surface 12a and the protrusion amount of the conductor 14 from the rear surface 12b of the protrusion 14b are preferably 30 nm to 500 nm, and the upper limit is more preferably 100 nm or less.
  • the insulating film 12 and the end of the conductive material such as metal are separated. It is preferable to selectively remove the insulating film and the anodic oxide film after processing so as to form the same plane.
  • heat treatment can be performed for the purpose of reducing the distortion in the conductor 14 caused by the metal filling.
  • the heat treatment is preferably performed in a reducing atmosphere from the viewpoint of suppressing metal oxidation.
  • the heat treatment is preferably performed at an oxygen concentration of 20 Pa or less, and more preferably in a vacuum.
  • vacuum refers to a state of space in which at least one of gas density and air pressure is lower than atmospheric pressure.
  • the heat treatment is preferably performed while applying stress to the insulating film 12 for the purpose of correction.
  • Step of forming resin layer For example, an inkjet method, a transfer method, a spray method, a screen printing method, or the like is used for the formation process of the resin layer 20 .
  • the ink jet method is preferable because the resin layer 20 is directly formed on the insulating film 12 and thus the process of forming the resin layer 20 can be simplified.
  • the resin layer 20 can be formed using, for example, a conventionally known surface protective tape applying device and laminator.
  • the resin layer is formed on the entire surface of the insulating film.
  • the resin material forming the resin layer 20 include ethylene copolymers, polyamide resins, polyester resins, polyurethane resins, polyolefin resins, acrylic resins, acrylonitrile resins, cellulose resins, and the like. of thermoplastic resins.
  • the resin layer 20 is preferably a peelable film with an adhesive layer, and is removed by heat treatment or ultraviolet exposure treatment. It is more preferable that the adhesive layer-attached film has weak adhesiveness and can be peeled off.
  • the adhesive layer-attached film described above is not particularly limited, and examples thereof include a heat peelable resin layer and an ultraviolet (UV) peelable resin layer.
  • the heat-peelable resin layer has adhesive strength at room temperature and can be easily peeled off only by heating.
  • specific examples of adhesives constituting the adhesive layer include rubber-based adhesives, acrylic-based adhesives, vinyl alkyl ether-based adhesives, silicone-based adhesives, polyester-based adhesives, and polyamide-based adhesives. , urethane adhesives, styrene-diene block copolymer adhesives, and the like.
  • the UV-releasable resin layer has a UV-curing adhesive layer, and loses its adhesive force upon curing, so that it can be detached.
  • the UV-curing adhesive layer examples include a base polymer into which a carbon-carbon double bond is introduced into the polymer side chain, the main chain, or at the end of the main chain.
  • a base polymer having a carbon-carbon double bond it is preferable to use an acrylic polymer as a basic skeleton.
  • the acrylic polymer is crosslinked, it can contain a polyfunctional monomer or the like as a monomer component for copolymerization, if necessary.
  • Base polymers with carbon-carbon double bonds can be used alone, but can also be blended with UV-curable monomers or oligomers. It is preferable to use a photopolymerization initiator in combination with the UV-curable adhesive layer in order to cure the adhesive layer by UV irradiation.
  • Benzoin ether-based compounds ketal-based compounds; aromatic sulfonyl chloride-based compounds; photoactive oxime-based compounds; benzophenone-based compounds; thioxanthone-based compounds; phosphonates and the like.
  • heat peelable resin layer Commercially available products of the heat peelable resin layer include, for example, Intelimer (registered trademark) tapes (manufactured by Nitta Corporation) such as WS5130C02 and WS5130C10; Somatac (registered trademark) TE series (manufactured by Somar Corporation); 3198, No. 3198LS, No. 3198M, no. 3198 MS, No. 3198H, No. 3195, No. 3196, No. 3195M, No. 3195 MS, No. 3195H, No. 3195HS, No. 3195V, No. 3195VS, No. 319Y-4L, No. 319Y-4LS, No. 319Y-4M, No. 319Y-4MS, no.
  • UV peelable resin layers examples include Elep Holder (registered trademark) (Nitto Denko Co., Ltd.); Adwill D-210, Adwill D-203, Adwill D-202, Adwill D-175, Adwill D-675 (all manufactured by Lintec Corporation); Sumilite (registered trademark) FLS N8000 series (Sumitomo Bakelite (manufactured by Furukawa Electric Co., Ltd.); UC353EP-110 (manufactured by Furukawa Electric Co., Ltd.);
  • commercial products of the UV peelable resin layer include, for example, ELP RF-7232DB, ELP UB-5133D (both manufactured by Nitto Denko Corporation); SP-575B-150, SP-541B-205, SP-537T. -160, SP-537T-230 (both manufactured by Furukawa Electric Co., Ltd.);
  • the adhesive layer-attached film described above can be attached using a known surface protection tape attaching device and laminator.
  • a resin composition containing an antioxidant material, a polymer material, a solvent (for example, methyl ethyl ketone, etc.), etc., which will be described later, is applied to the front and back surfaces of the insulating film. , drying, and, if necessary, firing.
  • the method of applying the resin composition is not particularly limited, and examples thereof include gravure coating, reverse coating, die coating, blade coating, roll coating, air knife coating, screen coating, bar coating, and curtain coating. conventionally known coating methods can be used.
  • the drying method after coating is not particularly limited. A heat treatment for ten minutes to several hours may be mentioned.
  • the method of baking after drying is not particularly limited because it varies depending on the polymer material used, but when using a polyimide resin, for example, a treatment such as heating at a temperature of 160 ° C. to 240 ° C. for 2 minutes to 60 minutes.
  • a treatment of heating at a temperature of 30° C. to 80° C. for 2 minutes to 60 minutes can be mentioned.
  • the composition shown below can also be used for the resin layer.
  • the composition of the resin layer will be described below.
  • the resin layer contains a polymer material and may contain an antioxidant material.
  • the polymer material contained in the resin layer is not particularly limited, but it can efficiently fill the gap between the object to be bonded such as a semiconductor chip or semiconductor wafer and the structure, and the adhesion between the structure and the semiconductor chip or semiconductor wafer can be improved.
  • Thermosetting resins are preferred because they are more durable.
  • Specific examples of thermosetting resins include epoxy resins, phenol resins, polyimide resins, polyester resins, polyurethane resins, bismaleimide resins, melamine resins, and isocyanate resins. Among them, it is preferable to use a polyimide resin and/or an epoxy resin for the reason that the insulation reliability is further improved and the chemical resistance is excellent.
  • benzotriazole and its derivatives are preferred.
  • Benzotriazole derivatives include hydroxyl groups, alkoxy groups (e.g., methoxy groups, ethoxy groups, etc.), amino groups, nitro groups, alkyl groups (e.g., methyl groups, ethyl groups, butyl groups, etc.) on the benzene ring of benzotriazole.
  • substituted benzotriazoles having halogen atoms eg, fluorine, chlorine, bromine, iodine, etc.
  • antioxidant material contained in the resin layer include general antioxidants such as higher fatty acids, higher fatty acid copper, phenol compounds, alkanolamines, hydroquinones, copper chelating agents, organic amines, organic ammonium salts and the like.
  • the content of the antioxidant material contained in the resin layer is not particularly limited, it is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, based on the total mass of the resin layer from the viewpoint of anticorrosion effect. Moreover, from the reason of obtaining suitable electrical resistance in this joining process, 5.0 mass % or less is preferable and 2.5 mass % or less is more preferable.
  • the resin layer contains a migration-preventing material for the reason that insulation reliability is further improved by trapping metal ions, halogen ions, and metal ions derived from the semiconductor chip and semiconductor wafer that may be contained in the resin layer. is preferred.
  • an anti-migration material for example, an ion exchanger, in particular a mixture of a cation exchanger and an anion exchanger, or only a cation exchanger can be used.
  • the cation exchanger and the anion exchanger can be appropriately selected from, for example, inorganic ion exchangers and organic ion exchangers, which will be described later.
  • inorganic ion exchangers include hydrous oxides of metals represented by hydrous zirconium oxide.
  • metal include, for example, zirconium, iron, aluminum, tin, titanium, antimony, magnesium, beryllium, indium, chromium, bismuth, and the like.
  • zirconium-based materials have the ability to exchange cations Cu 2+ and Al 3+ .
  • Iron-based materials also have exchangeability with respect to Ag + and Cu 2+ .
  • tin-based, titanium-based, and antimony-based are cation exchangers.
  • bismuth-based materials have an exchange ability with respect to anion Cl.sup.- .
  • zirconium-based materials exhibit anion exchange ability depending on the manufacturing conditions. The same applies to aluminum-based and tin-based materials.
  • inorganic ion exchangers acid salts of polyvalent metals typified by zirconium phosphate, heteropolyacid salts typified by ammonium molybdophosphate, and synthetic compounds such as insoluble ferrocyanides are known. Some of these inorganic ion exchangers are already commercially available, for example, various grades of Toagosei Co., Ltd. under the trade name IXE are known.
  • natural zeolites or powders of inorganic ion exchangers such as montmorillonite can also be used.
  • Organic ion exchangers include crosslinked polystyrene with sulfonic acid groups as cation exchangers, and also those with carboxylic acid, phosphonic acid or phosphinic acid groups.
  • crosslinked polystyrene having a quaternary ammonium group, a quaternary phosphonium group or a tertiary sulfonium group can be used as an anion exchanger.
  • inorganic ion exchangers and organic ion exchangers may be appropriately selected in consideration of the types of cations and anions to be captured and the exchange capacity for the ions. Needless to say, inorganic ion exchangers and organic ion exchangers may be mixed and used. Inorganic ion exchangers are preferred because the manufacturing process of electronic devices includes a heating process.
  • the mixing ratio of the ion exchanger and the above-described polymer material is preferably 10% by mass or less for the ion exchanger, and 5% by mass or less for the ion exchanger, from the viewpoint of mechanical strength. More preferably, the content of the ion exchanger is 2.5% by mass or less. Moreover, from the viewpoint of suppressing migration when a semiconductor chip or semiconductor wafer and a structure are bonded, the content of the ion exchanger is preferably 0.01% by mass or more.
  • the resin layer preferably contains an inorganic filler.
  • the inorganic filler is not particularly limited and can be appropriately selected from known ones. , crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, aluminum nitride, zirconium oxide, yttrium oxide, silicon carbide, silicon nitride and the like.
  • the average particle size of the inorganic filler is preferably larger than the interval between the conducting paths.
  • the average particle size of the inorganic filler is preferably 30 nm to 10 ⁇ m, more preferably 80 nm to 1 ⁇ m.
  • the average particle size is defined as the primary particle size measured by a laser diffraction/scattering particle size measuring device (Microtrac MT3300 manufactured by Nikkiso Co., Ltd.).
  • the resin layer may contain a curing agent.
  • a curing agent When a curing agent is contained, from the viewpoint of suppressing poor bonding with the surface shape of the semiconductor chip or semiconductor wafer to be connected, a curing agent that is solid at normal temperature is not used, and a curing agent that is liquid at normal temperature is contained. is more preferred.
  • solid at room temperature refers to a substance that is solid at 25°C, for example, a substance that has a melting point higher than 25°C.
  • curing agents include aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone, aliphatic amines, imidazole derivatives such as 4-methylimidazole, dicyandiamide, tetramethylguanidine, thiourea-added amines, methyl Carboxylic acid anhydrides such as hexahydrophthalic anhydride, carboxylic acid hydrazides, carboxylic acid amides, polyphenol compounds, novolac resins, polymercaptans, etc. can be mentioned, and from these curing agents, those which are liquid at 25°C are appropriately selected. can be used
  • the curing agent may be used singly or in combination of two or more.
  • the resin layer may contain various additives such as dispersing agents, buffering agents, viscosity modifiers, etc. that are commonly added to the resin insulating film of semiconductor packages within the range that does not impair its characteristics.
  • the resin layer in addition to the above, for example, one containing a main composition containing an acrylic polymer, an acrylic monomer, and a maleimide compound shown below can be used.
  • the acrylic polymer is a polymer containing structural units derived from a (meth)acrylate component, and preferably does not make the resin layer too tacky and does not impair the workability in the semiconductor mounting process.
  • (Meth)acrylate components include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, butoxyethyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, Lauryl (meth)acrylate and the like
  • the acrylic polymer may further contain structural units corresponding to other monomer components copolymerizable with the (meth)acrylate component described above.
  • examples of other monomer components include carboxyl group-containing monomers (e.g., (meth)acrylic acid), epoxy group-containing monomers (e.g., glycidyl (meth)acrylate), and nitrile group-containing monomers (e.g., acrylonitrile, etc.). can be done.
  • acrylic polymers that contain structural units corresponding to butyl acrylate, methyl acrylate, acrylic acid, glycidyl methacrylate, and acrylonitrile can be used.
  • the acrylic polymer can be obtained by polymerizing the above-mentioned (meth)acrylate component or other monomer components.
  • Polymerization methods include solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like.
  • Examples of the types of acrylic polymer polymerization reactions include radical polymerization, cationic polymerization, anionic polymerization, living radical polymerization, living cationic polymerization, living anionic polymerization, and coordination polymerization.
  • the weight-average molecular weight (Mw) of the acrylic polymer is not particularly limited, but can be, for example, in the range of 100,000 or more and 1,200,000 or less, or in the range of 500,000 or more and 1,000,000 or less.
  • the acrylic polymer is contained in the range of 10 parts by mass or more and 60 parts by mass or less in 100 parts by mass of the main composition. preferably 10 parts by mass or more and 45 parts by mass or less, more preferably 15 parts by mass or more and 40 parts by mass or less. If the acrylic polymer content is less than 10 parts by mass, it tends to be difficult to eliminate voids. Moreover, when the content of the acrylic polymer exceeds 60 parts by mass, it tends to be difficult to achieve low-pressure mounting, and the connectivity tends to deteriorate.
  • acrylic polymer one type of acrylic polymer may be contained alone in the main composition, or two or more types of acrylic polymer may be used in combination.
  • the total content of the acrylic polymers in the resin layer is preferably within the above range.
  • Acrylic monomers include isocyanuric acid EO-modified diacrylate (manufactured by Toagosei Co., Ltd.), isocyanuric acid EO-modified triacrylate (manufactured by Toagosei Co., Ltd.), dipentaerythritol and tetraacrylate (manufactured by Toagosei Co., Ltd.), 2 -Hydroxy-3-phenoxypropyl acrylate (manufactured by Toagosei Co., Ltd.), 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene (manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethanol Acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethanol Acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd
  • the acrylic monomer in the resin layer is contained in the range of 10 parts by mass or more and 60 parts by mass or less, preferably in the range of 10 parts by mass or more and 55 parts by mass or less, in 100 parts by mass of the main composition. Preferably, it can be contained in the range of 10 parts by mass or more and 50 parts by mass or less. If the content of the acrylic monomer is less than 10 parts by mass, the connectivity tends to deteriorate. Moreover, when the content of the acrylic monomer exceeds 60 parts by mass, it tends to be difficult to eliminate voids.
  • the acrylic monomer may contain one type of acrylic monomer alone, or may contain two or more types of acrylic monomers in combination. When two or more acrylic monomers are used in combination, the total content of the acrylic monomers in the resin layer is preferably within the above range.
  • maleimide compound for example, a compound having two or more maleimide groups in one molecule can be used, and bismaleimide is preferred.
  • maleimide compounds include 4-methyl-1,3-phenylenebismaleimide, 4,4-bismaleimide diphenylmethane, m-phenylenebismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'. -diethyl-4,4'-diphenylmethanebismaleimide and the like.
  • aromatic bismaleimides are preferable, and in particular, 3,3'-dimethyl-5,5'-diethyl-4, which has good solvent solubility or flowability, considering workability in the process of producing the resin layer.
  • 4'-diphenylmethanebismaleimide is preferred.
  • the maleimide compound in the resin layer is contained in the range of 20 parts by mass or more and 70 parts by mass or less, preferably in the range of 20 parts by mass or more and 60 parts by mass or less, in 100 parts by mass of the main composition. It is preferably contained in the range of 20 parts by mass or more and 55 parts by mass or less. If the content of the maleimide compound is less than 20 parts by mass, it tends to be difficult to achieve low-pressure mounting, and the connectivity tends to deteriorate. Moreover, when the content of the maleimide compound exceeds 70 parts by mass, low-pressure mounting and voidless mounting tend to become difficult.
  • the composition used for the resin layer may further contain components other than the components constituting the main composition described above.
  • Other components include, for example, phenolic compounds and fillers.
  • Phenolic compounds can be used as curing agents for the maleimide compounds described above, but the thermosetting reaction can be initiated without phenol.
  • phenol compound for example, allylated bisphenol can be used.
  • 2,2′-diallylbisphenol A product name: DABPA
  • 4,4′-(dimethylmethylene)bis[2-(2-propenyl)-6-methylphenol] etc.
  • 2,2'-diallylbisphenol A is preferred.
  • the content of the phenolic compound can be, for example, 15 parts by mass or less with respect to 100 parts by mass in total of the acrylic polymer, the acrylic monomer, the maleimide compound, and the phenolic compound.
  • the phenol compound one type of phenol compound may be contained alone, or two or more types of phenol compounds may be used in combination.
  • the total content of the phenolic compounds in the resin layer is preferably within the above range.
  • fillers inorganic fillers, organic fillers, conductive particles, and the like can be used.
  • an inorganic filler for example, silica filler
  • the content of the filler can be, for example, 30 parts by mass or less with respect to 100 parts by mass in total of the acrylic polymer, the acrylic monomer, the maleimide compound, and the filler.
  • the filler one type of filler may be contained alone, or two or more types of filler may be used in combination.
  • the total content of the fillers in the resin layer is preferably within the above range.
  • an inkjet method, a transfer method, a spray method, a screen printing method, or the like is used for the formation process of the protective layer 22 .
  • the inkjet method is preferable because the protective layer 22 is formed directly on the resin layer 20, and the process for forming the protective layer 22 can be simplified.
  • the protective layer 22 can be formed using, for example, a conventionally known surface protective tape applying device and laminator.
  • coating the above-mentioned protective layer forming composition on the surface of a resin film, drying it, and baking as needed, etc. are mentioned.
  • the method of applying the protective layer-forming composition is not particularly limited, and examples thereof include gravure coating, reverse coating, die coating, blade coating, roll coating, air knife coating, screen coating, bar coating, and curtain coating.
  • a conventionally known coating method such as a method can be used.
  • FIG. 13 is a schematic diagram showing an example of a joined body according to an embodiment of the present invention.
  • the laminated device 40 shown in FIG. 13 shows an example of a bonded body.
  • the structure 10 described above (see FIG. 1) is used as the anisotropic conductive member 45 exhibiting anisotropic conductivity.
  • the laminated device has a conductive member having a conductive portion having conductivity and an anisotropically conductive member, and is joined by bringing the conductive portion and the protruding portion of the anisotropically conductive member into contact with each other. .
  • the 13 is, for example, a semiconductor element 42, an anisotropically conductive member 45, and a semiconductor element 44 that are bonded and electrically connected in this order in the lamination direction Ds.
  • the anisotropically conductive member 45 the conductors 14 (see FIG. 1) are arranged parallel to the stacking direction Ds and have conductivity in the stacking direction Ds.
  • the semiconductor element 42, the anisotropically conductive member 45, and the semiconductor element 44 that are stacked together constitute the joined body 41.
  • the stacked device 40 has a form in which one semiconductor element 44 is bonded to one semiconductor element 42, but is not limited to this. A configuration in which three semiconductor elements (not shown) are joined via an anisotropically conductive member 45 is also possible.
  • a laminated device is configured by three semiconductor elements and two anisotropically conductive members 45 .
  • the semiconductor element 42 , the anisotropically conductive member 45 , the semiconductor element 44 , the anisotropically conductive member 45 , and the semiconductor element 46 that are stacked together constitute the joined body 41 .
  • the semiconductor element is a conductive member having a conductive portion.
  • a conductive member having a conductive portion having conductivity is not limited to a semiconductor element, and may be a substrate having an electrode. Substrates having electrodes are, for example, wiring substrates and interposers.
  • the form of the stacked device is not particularly limited. Scale Package), TSV (Through Silicon Via), and the like.
  • Stacked device 40 may have a semiconductor element that functions as an optical sensor.
  • a semiconductor element and a sensor chip (not shown) are stacked in the stacking direction Ds.
  • the sensor chip may be provided with a lens.
  • the semiconductor element is formed with a logic circuit, and the configuration is not particularly limited as long as the signal obtained by the sensor chip can be processed.
  • the sensor chip has an optical sensor that detects light.
  • the optical sensor is not particularly limited as long as it can detect light, and for example, a CCD (Charge Coupled Device) image sensor or a CMOS (Complementary Metal Oxide Semiconductor) image sensor is used.
  • the configuration of the lens is not particularly limited as long as it can focus light on the sensor chip, and for example, a so-called microlens is used.
  • a joined body is obtained by joining a conductive member including a conductive portion having conductivity and a structure.
  • the bonded object becomes a device.
  • semiconductor elements are exemplified as bonding objects of structures, but for example, they have electrodes or element regions.
  • Examples of those having electrodes include, for example, semiconductor elements that perform a specific function by themselves, but also include those that perform a specific function when a plurality of elements are assembled.
  • wiring members and the like that only transmit electrical signals are included, and printed wiring boards and the like are also included in those having electrodes.
  • the device region is a region in which various device configuration circuits and the like are formed for functioning as an electronic device.
  • MEMS Micro Electro Mechanical Systems
  • MEMS Micro Electro Mechanical Systems
  • MEMS include, for example, sensors, actuators and antennas.
  • Sensors include, for example, various sensors such as acceleration, sound, and light.
  • an element configuration circuit and the like are formed, and electrodes (not shown) are provided for electrically connecting the semiconductor chip to the outside.
  • the element region has an electrode region in which electrodes are formed. Note that the electrodes in the element region are, for example, Cu posts.
  • An electrode area is basically an area that includes all electrodes formed. However, if the electrodes are discretely provided, the area where each electrode is provided is also called the electrode area.
  • the structure may be in the form of individual pieces such as semiconductor chips, in the form of semiconductor wafers, or in the form of wiring layers.
  • the structure is bonded to an object to be bonded, but the object to be bonded is not particularly limited to the above-described semiconductor elements and the like. For example, semiconductor elements in wafer state, semiconductor elements in chip state, printed wiring A plate, a heat sink, and the like are objects to be bonded.
  • the semiconductor element 42 and the semiconductor element 44 described above are, in addition to those described above, for example, logic LSI (Large Scale Integration) (for example, ASIC (Application Specific Integrated Circuit), FPGA (Field Programmable Gate Array), ASSP (Application Specific Standard Product), etc.), microprocessors (e.g., CPU (Central Processing Unit), GPU (Graphics Processing Unit), etc.), memory (e.g., DRAM (Dynamic Random Access Memory), HMC (Hybrid Memory Cube), MRAM (MagneticRAM: magnetic memory), PCM (Phase-Change Memory), ReRAM (Resistive RAM), FeRAM (Ferroelectric RAM), flash memory (NAND (Not AND) flash), etc.) , LED (Light Emitting Diode), (e.g., microflash of mobile terminal, automotive, projector light source, LCD backlight, general lighting, etc.), power device, analog IC (Integrated Circuit), (e.g., DC
  • a semiconductor element is, for example, a complete one, and a single semiconductor element exerts a specific function such as a circuit or a sensor.
  • the semiconductor element may have an interposer function.
  • it is possible to stack a plurality of devices such as a logic chip having a logic circuit and a memory chip on a device having an interposer function.
  • the devices can be joined.
  • the laminated device is not limited to the one-to-plural form in which a plurality of semiconductor elements are joined to one semiconductor element, but a form in which a plurality of semiconductor elements are joined to a plurality of semiconductor elements. Certain many-to-many forms are also possible.
  • the present invention is basically configured as described above. Although the structure, the method for producing an anisotropically conductive member, and the composition for forming a protective layer according to the present invention have been described in detail above, the present invention is not limited to the above-described embodiments and does not depart from the gist of the present invention. Of course, various improvements or changes may be made within the scope.
  • Processing was performed so that 100 individual pieces of 2 ⁇ 4 mm could be secured from the structure.
  • the degree of adhesion of chips to the resin layer was examined by SEM (scanning electron microscope) and visually.
  • SEM scanning electron microscope
  • the degree of adherence of shavings to the resin layer was examined by SEM and visual observation.
  • the degree of adhesion of cutting debris to the resin layer by SEM 10 fields of view were observed at the same magnification, the number of cutting debris was counted, and the total of cutting debris in 10 fields of view was obtained. The magnification was 20,000 times.
  • Example 1 The structure of Example 1 will be described.
  • [Structure] ⁇ Production of aluminum substrate> Si: 0.06% by mass, Fe: 0.30% by mass, Cu: 0.005% by mass, Mn: 0.001% by mass, Mg: 0.001% by mass, Zn: 0.001% by mass, Ti: 0.03% by mass, and the balance is Al and inevitable impurities.
  • Molten metal is prepared using an aluminum alloy, and after performing molten metal treatment and filtration, an ingot with a thickness of 500 mm and a width of 1200 mm is DC (Direct Chill ) was produced by the casting method.
  • the aluminum substrate was finished to a thickness of 1.0 mm by cold rolling to obtain an aluminum substrate of JIS 1050 material. After this aluminum substrate was made to have a width of 1030 mm, it was subjected to the following treatments.
  • ⁇ Electropolishing treatment> The aluminum substrate described above was subjected to electropolishing treatment using an electropolishing solution having the following composition under conditions of a voltage of 25 V, a solution temperature of 65° C., and a solution flow rate of 3.0 m/min.
  • a carbon electrode was used as the cathode, and GP0110-30R (manufactured by Takasago Seisakusho Co., Ltd.) was used as the power source.
  • the flow velocity of the electrolytic solution was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE Corporation).
  • the electrolytically polished aluminum substrate was anodized by a self-ordering method according to the procedure described in JP-A-2007-204802. After electropolishing, the aluminum substrate was pre-anodized for 5 hours with an electrolytic solution of 0.50 mol/L oxalic acid under the conditions of a voltage of 40 V, a liquid temperature of 16° C., and a liquid flow rate of 3.0 m/min. . After that, the pre-anodized aluminum substrate was subjected to film removal treatment by immersing it in a mixed aqueous solution of 0.2 mol/L chromic anhydride and 0.6 mol/L phosphoric acid (liquid temperature: 50° C.) for 12 hours.
  • an electrolytic solution of 0.50 mol/L oxalic acid was applied for 3 hours and 45 minutes under the conditions of a voltage of 40 V, a solution temperature of 16° C., and a solution flow rate of 3.0 m/min. An oxide film was obtained.
  • a stainless steel electrode was used as the cathode, and GP0110-30R (manufactured by Takasago Seisakusho Co., Ltd.) was used as the power source.
  • NeoCool BD36 manufactured by Yamato Scientific Co., Ltd.
  • Pair Stirrer PS-100 manufactured by EYELA Tokyo Rikakikai Co., Ltd.
  • the flow velocity of the electrolyte was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE Corporation).
  • etching treatment is performed by immersing the anodized film at 30° C. for 150 seconds in an alkaline aqueous solution prepared by dissolving zinc oxide in an aqueous sodium hydroxide solution (50 g/l) to a concentration of 2000 ppm.
  • the barrier layer at the bottom of the micropores was removed and zinc was simultaneously deposited on the exposed surface of the aluminum substrate.
  • the average thickness of the anodized film after the barrier layer removal step was 30 ⁇ m.
  • ⁇ Metal filling process> electrolytic plating was performed using the aluminum substrate as a cathode and platinum as a positive electrode. Specifically, a metal-filled microstructure having micropores filled with nickel was produced by performing constant-current electrolysis using a copper plating solution having the composition shown below.
  • the constant current electrolysis uses a plating apparatus manufactured by Yamamoto Plating Tester Co., Ltd., a power supply (HZ-3000) manufactured by Hokuto Denko Co., Ltd., and performs cyclic voltammetry in the plating solution to deposit. After confirming the potential, the treatment was performed under the conditions shown below.
  • the surface of the anodized film after filling the micropores with metal was observed using a field emission scanning electron microscope (FE-SEM), and the presence or absence of sealing by metal in 1000 micropores was observed and sealed.
  • the porosity (the number of closed micropores/1000) was calculated and found to be 98%.
  • the anodized film after filling the metal in the micropores is cut in the thickness direction using a focused ion beam (FIB), and the cross section is observed with a field emission scanning electron microscope (FE-SEM).
  • a photograph of the surface (magnification: 50,000 times) was taken using the micropores to check the inside of the micropores, and it was found that the insides of the sealed micropores were completely filled with metal.
  • ⁇ Substrate removal step> Then, the aluminum substrate was dissolved and removed by immersion in a mixed solution of copper chloride/hydrochloric acid to fabricate a metal-filled microstructure having an average thickness of 30 ⁇ m.
  • the diameter of the vias in the fabricated metal-filled microstructure was 60 nm, the pitch between vias was 100 nm, and the density of vias was 57.7 million/mm 2 .
  • the metal-filled microstructure was immersed in an aqueous sodium hydroxide solution (concentration: 5% by mass, liquid temperature: 20°C), and the immersion time was adjusted so that the height of the protrusions was 300 nm.
  • the surface of the aluminum anodized film was selectively dissolved, then washed with water and dried to protrude the copper cylinders as the conducting paths.
  • a copper column as a conductive path was projected so that the height of the projected portion was 300 nm.
  • ⁇ Resin layer forming step> A resin layer having a thickness of 0.5 ⁇ m was formed on both surfaces of the anodized film using a resin.
  • the resin layer was formed using a solution of 20 g of thermosetting resin BST001A (manufactured by Namics Co., Ltd.) and 180 g of diethylene glycol diethyl ether.
  • ⁇ Protective layer forming step> A protective layer having a thickness of 1 ⁇ m was formed on the surface of the resin layer using PVA (GOHSENOL (trade name), Mitsubishi Chemical Corporation).
  • the oxygen permeability coefficient of the protective layer is shown in Table 1 below.
  • STP oxygen permeability coefficient
  • the coating layer is a combination of the resin layer, the intermediate layer and the protective layer.
  • a configuration of a resin layer and a protective layer without an intermediate layer is also a coating layer.
  • hot water at a temperature of 40° C. was used as a solvent for the removing liquid to dissolve and remove the protective layer. Dissolution removal time was 5 minutes.
  • Example 2 was the same as Example 1 except that a protective layer having a thickness of 2 ⁇ m was formed using PVDC (polyvinylidene chloride). Saran Resin F216 (trade name, Asahi Kasei Corporation) was used for PVDC.
  • a mixed solution of tetrahydrofuran (THF) and toluene (TOL) was used as a solvent for the removing liquid to dissolve and remove the protective layer.
  • the mixing ratio of tetrahydrofuran (THF) and toluene (TOL) was set to 2:1, and the temperature of the mixture was set to 25°C. Moreover, the dissolution removal time was 1 minute.
  • Example 3 was the same as Example 1 except that an intermediate layer was provided between the resin layer and the protective layer.
  • the intermediate layer was formed using a fluororesin.
  • a fluoroethylene vinyl ether alternating copolymer (Lumiflon (registered trademark) LF200 (trade name, manufactured by AGC Inc.)) was further diluted 10-fold with xylene and spin-coated to form a film on the resin layer. did.
  • the protective layer was dissolved and removed in the same manner as in Example 1.
  • Example 4 differs from Example 1 in that an intermediate layer is provided between the resin layer and the protective layer, and that the protective layer is formed using PVDC. was the same as In Example 4, the intermediate layer was formed using PVA. The intermediate layer was formed in the same manner as the protective layer of Example 1. The protective layer was formed using Saran Resin F310 (trade name, Asahi Kasei Corporation). In Example 4, the protective layer was removed by dissolution using methyl ethyl ketone (MEK) at a temperature of 25° C. as a solvent for the removing liquid. Dissolution removal time was 1 minute.
  • Example 5 differs from Example 1 in that an intermediate layer is provided between the resin layer and the protective layer, and that the protective layer is made of epoxy resin.
  • Example 5 the intermediate layer was formed using a fluororesin. The intermediate layer was formed in the same manner as the protective layer in Example 3. The protective layer was formed with a thickness of 3 ⁇ m using Maxieve (trade name, manufactured by Mitsubishi Gas Chemical Company, Inc.). In Example 5, the protective layer was removed by delamination, which is physical peeling.
  • Example 6 differs from Example 1 in that an intermediate layer is provided between the resin layer and the protective layer, and that the protective layer is made of a laminate film. assumed to be the same.
  • a protective layer having a thickness of 1.4 ⁇ m was formed using a PVDC coated film (V Barrier (registered trademark, manufactured by Mitsui Chemicals Tohcello, Inc.)).
  • the base layer of PVDC-coated film becomes the intermediate layer.
  • the protective layer was removed by delamination, which is physical peeling. In this case, peeling occurred between the base layer and the resin layer.
  • Example 7 differs from Example 1 in that an intermediate layer is provided between the resin layer and the protective layer, and that the protective layer is made of a laminate film.
  • Example 7 a protective layer having a thickness of 1.2 ⁇ m was formed using a PVDC coated film (Bonyl-K PC (Kohjin Film & Chemicals Co., Ltd.)). A nylon film (base layer) of a PVDC-coated film serves as an intermediate layer.
  • the protective layer was removed by delamination, which is physical peeling. In this case, peeling occurred between the base layer and the resin layer.
  • the mixed solution had a ratio of ethyl acetate and hexane of 50:50 by mass.
  • a protective layer is applied to a Si wafer to a film thickness of 10 ⁇ m or more, immersed in a mixed solvent at a temperature of 25° C. for 5 seconds, then thoroughly washed off the surface solvent with ethanol, washed with running water, and dried. did.
  • the change in thickness before and after the treatment was measured using a non-contact film thickness gauge to calculate the dissolution rate. This calculated dissolution rate indicates the solubility in ethyl acetate.
  • Adhesion between the protective layer and the layer immediately below it was evaluated by sticking a 25 mm wide tape on the protective layer and peeling it off at 180° according to the method of JIS K 6854-2.
  • Comparative Example 1 Comparative Example 1 was the same as Example 1 except that the resin layer and the protective layer were not provided in Comparative Example 1.
  • Comparative example 2 Comparative Example 2 was the same as Example 1 except that the protective layer was not provided in Comparative Example 1.
  • Comparative Example 1 has a structure without a resin layer, an intermediate layer and a protective layer, and a large amount of shavings adhered after washing. Comparative Example 2 had no intermediate layer and no protective layer, and had only a resin layer, and after washing, a considerable amount of cutting debris adhered.
  • Example 1 and Example 2 From Example 1 and Example 2, the evaluation of the degree of attachment of cutting debris after removal of the protective layer was better when PVA was used as the protective layer than when PVDC was used. From Example 1 and Example 3, the provision of the intermediate layer composed of the fluororesin gave a better evaluation of the degree of attachment of cutting debris after removal of the protective layer.
  • anisotropically conductive member 12 insulating film 12a front surface 12b rear surface 13 pore 14 conductor 14a, 14b protrusion 15 anodized film 16 anisotropic conductive layer 20 resin layer 20a, 22a surface 22 protective layer 30 aluminum substrate 30a surface 31 Barrier layer 32c Bottom 32d Surface 35 Metal 35a Metal layer 35b Metal 36 Thermal release layer 37 Support 38 Dicing tape 40 Stacked device 41 Joined body 42, 44 Semiconductor element 45 Anisotropically conductive member Ds Stacking direction Dt Thickness direction d Average diameter H Height hm, hj Average thickness ht Thickness p Distance between centers

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US20220165619A1 (en) * 2019-08-16 2022-05-26 Fujifilm Corporation Method for manufacturing structure
WO2024190271A1 (ja) * 2023-03-13 2024-09-19 富士フイルム株式会社 半導体デバイス

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