WO2016063908A1 - Composition adhésive photosensible et dispositif à semi-conducteur - Google Patents

Composition adhésive photosensible et dispositif à semi-conducteur Download PDF

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Publication number
WO2016063908A1
WO2016063908A1 PCT/JP2015/079691 JP2015079691W WO2016063908A1 WO 2016063908 A1 WO2016063908 A1 WO 2016063908A1 JP 2015079691 W JP2015079691 W JP 2015079691W WO 2016063908 A1 WO2016063908 A1 WO 2016063908A1
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Prior art keywords
adhesive composition
photosensitive adhesive
composition according
norbornene
photosensitive
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PCT/JP2015/079691
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English (en)
Japanese (ja)
Inventor
広道 杉山
誠 堀井
一義 藤田
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住友ベークライト株式会社
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Priority to JP2016555251A priority Critical patent/JPWO2016063908A1/ja
Publication of WO2016063908A1 publication Critical patent/WO2016063908A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J145/00—Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
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    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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    • H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
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    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
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    • H01L2224/32135—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
    • H01L2224/32145—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being stacked
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    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
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    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
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    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
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    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/49—Structure, shape, material or disposition of the wire connectors after the connecting process of a plurality of wire connectors
    • H01L2224/491—Disposition
    • H01L2224/4911—Disposition the connectors being bonded to at least one common bonding area, e.g. daisy chain
    • H01L2224/49113—Disposition the connectors being bonded to at least one common bonding area, e.g. daisy chain the connectors connecting different bonding areas on the semiconductor or solid-state body to a common bonding area outside the body, e.g. converging wires
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    • H01L2224/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L2224/80 - H01L2224/90
    • H01L2224/92—Specific sequence of method steps
    • H01L2224/922—Connecting different surfaces of the semiconductor or solid-state body with connectors of different types
    • H01L2224/9222—Sequential connecting processes
    • H01L2224/92242—Sequential connecting processes the first connecting process involving a layer connector
    • H01L2224/92247—Sequential connecting processes the first connecting process involving a layer connector the second connecting process involving a wire connector
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    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
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    • H01L2924/15311—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA
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    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Definitions

  • the present invention relates to a photosensitive adhesive composition and a semiconductor device.
  • an adhesive film for die bonding is disposed between the semiconductor elements, thereby bonding the semiconductor elements together.
  • a buffer coat film is provided between the semiconductor element and the adhesive in consideration of the stress accompanying the curing shrinkage of the adhesive occurring at the interface between the semiconductor element and the adhesive. Thereby, relaxation of stress concentration at the interface between the semiconductor element and the adhesive is achieved.
  • Patent Document 1 discloses a stack package in which a plurality of semiconductor elements are stacked.
  • a surface protective layer such as a buffer coat film is formed between a wafer and a die bonding film (die attach film).
  • An object of the present invention is to provide a photosensitive adhesive composition capable of adhering semiconductor elements while relaxing stress concentration, and a laminated semiconductor element in which semiconductor elements are adhered to each other by such a photosensitive adhesive composition.
  • An object of the present invention is to provide a semiconductor device that is highly producible and easy to manufacture.
  • a photosensitive adhesive composition used for joining a semiconductor element and a member to be joined The elastic modulus at 25 ° C. of the photosensitive adhesive composition after curing is 2.0 to 3.5 GPa, The elastic modulus at 25 ° C. of the photosensitive adhesive composition before curing is 70 to 120% of the elastic modulus at 25 ° C. of the photosensitive adhesive composition after curing,
  • the adhesive strength of the photosensitive adhesive composition before being subjected to etching treatment and ashing treatment before curing to a semiconductor element at 25 ° C. is 20 to 200 N
  • a photosensitive adhesive composition, wherein the photosensitive adhesive composition before curing has a minimum melt viscosity at 100 to 200 ° C. of 20 to 500 Pa ⁇ s.
  • the semiconductor element includes a terminal and a film covering the terminal,
  • the etching process uses a mixed gas of fluorine compound gas (CF 4 ), argon gas (Ar), and oxygen gas (O 2 ), output: 2500 W, time: 6 minutes, CF 4 flow rate / Ar Flow rate / O 2 flow rate:
  • CF 4 fluorine compound gas
  • Ar argon gas
  • O 2 oxygen gas
  • the ashing process is performed using a mixed gas of oxygen gas (O 2 ) and argon gas (Ar) under the conditions of output: 600 W, time: 12 minutes, O 2 flow rate / Ar flow rate: 50 sccm / 150 sccm.
  • the photosensitive adhesive composition according to any one of (1) to (3), which is performed.
  • the adhesive strength at 25 ° C. of the photosensitive adhesive composition before being subjected to the etching treatment and the ashing treatment to the UV peeling type back grind film is 3.0 N / 25 mm or more.
  • the photosensitive adhesive composition in any one of (4).
  • the photosensitive adhesive composition according to any one of (1) to (5), which is 0.5 N / 25 mm or less.
  • z is an integer of 1 or more and 10 or less.
  • a semiconductor device comprising a stacked semiconductor element, The laminated semiconductor element is provided between a plurality of semiconductor elements and the semiconductor elements, and the cured product of the photosensitive adhesive composition according to any one of (1) to (18), which joins the semiconductor elements.
  • a semiconductor device comprising:
  • a photosensitive adhesive composition capable of adhering semiconductor elements while relaxing stress concentration can be obtained.
  • a highly reliable semiconductor device including a stacked semiconductor element can be obtained.
  • FIG. 1 is a cross-sectional view showing an embodiment of a semiconductor device of the present invention.
  • FIG. 2 is a diagram for explaining a method of manufacturing the semiconductor device of the present invention.
  • FIG. 3 is a diagram for explaining a method of manufacturing the semiconductor device of the present invention.
  • FIG. 4 is a diagram for explaining a method of manufacturing the semiconductor device of the present invention.
  • FIG. 1 is a cross-sectional view showing an embodiment of a semiconductor device of the present invention.
  • a semiconductor device 10 shown in FIG. 1 is an example having a BGA (Ball Grid Array) type semiconductor package.
  • the semiconductor device 10 includes a plurality of stacked semiconductor chips (semiconductor elements) 20, an adhesive layer 601 that bonds the semiconductor chips 20 together, a package substrate 30 that supports the semiconductor chips 20, a semiconductor chip 20, and a package substrate 30.
  • An adhesive layer 101 for bonding the semiconductor chip 20, a mold part 50 for sealing the semiconductor chip 20, and a solder ball 80 provided below the package substrate 30.
  • the configuration of each unit will be described in detail.
  • the semiconductor chip 20 may be any kind of element, for example, a memory element such as a NAND (NotDRAMAND) flash memory, a DRAM (Dynamic ⁇ Random Access Memory), an IC (Integrated Circuit), or an LSI (Large Scale Integration). Such an integrated circuit element is mentioned.
  • a memory element such as a NAND (NotDRAMAND) flash memory, a DRAM (Dynamic ⁇ Random Access Memory), an IC (Integrated Circuit), or an LSI (Large Scale Integration).
  • a memory element such as a NAND (NotDRAMAND) flash memory, a DRAM (Dynamic ⁇ Random Access Memory), an IC (Integrated Circuit), or an LSI (Large Scale Integration).
  • the constituent material of the semiconductor chip 20 is not particularly limited, and examples thereof include single crystal materials such as silicon and silicon carbide, polycrystalline materials, and amorphous materials.
  • the plurality of semiconductor chips 20 are stacked slightly shifted from each other in the in-plane direction, thereby forming a chip stacked body 200 (stacked semiconductor element).
  • the semiconductor chips 20 are bonded to each other through an adhesive layer 601.
  • the adhesive layer 601 is also provided on the upper surface of the chip stack 200.
  • a package substrate 30 shown in FIG. 1 is a build-up substrate including a core substrate 31, an insulating layer 32, a solder resist layer 33, wirings 34, and conductive vias 35.
  • the core substrate 31 is a substrate that supports the package substrate 30 and is made of, for example, a composite material in which a glass cloth is filled with a resin material.
  • the insulating layer 32 is an interlayer insulating layer that insulates the wirings 34 from each other and the wiring 34 and the conductive via 35, and is made of, for example, a resin material.
  • the solder resist layer 33 is a surface protective layer that protects the wiring formed on the outermost surface of the package substrate 30, and is made of, for example, a resin material.
  • the wiring 34 and the conductive via 35 are each an electric signal transmission path, and are made of, for example, a metal material such as Au, Ag, Cu, Al, Ni alone or an alloy.
  • the solder ball 80 is electrically connected to the wiring 34, and functions as an electrode for connecting the wiring 34 to another electric circuit by being fused to an external electric circuit.
  • a chip stack 200 formed by stacking a plurality of semiconductor chips 20 is placed on the upper surface of the package substrate 30.
  • the chip stack 200 and the package substrate 30 are bonded together by an adhesive layer 101.
  • a part of the wiring 34 of the package substrate 30 is exposed on the upper surface of the package substrate 30 to constitute an exposed portion.
  • the exposed portion and the electrode portion of each semiconductor chip 20 are connected by a bonding wire 70.
  • Such a mold part 50 is comprised with various resin materials, such as an epoxy resin and a phenol resin, for example.
  • FIGS. 1 to 4 are diagrams for explaining a method of manufacturing the semiconductor device of the present invention.
  • the method for producing a semiconductor device of the present invention includes a coating step of applying a liquid containing a photosensitive adhesive composition on a wafer to obtain a coating film, an exposure step of exposing the obtained coating film, and unexposed by development. Development process to remove the coating film on the surface, processing process to etch and ash the wafer through the opening formed in the coating film, back grinding process to grind the back surface of the wafer, and dicing the wafer A dicing process for dividing the semiconductor chip into pieces, picking up the semiconductor chip and mounting it on the package substrate, and then picking up another semiconductor chip and pressing it onto the semiconductor chip (member to be joined) mounted first A mounting step.
  • a coating step of applying a liquid containing a photosensitive adhesive composition on a wafer to obtain a coating film to obtain a coating film
  • an exposure step of exposing the obtained coating film and unexposed by development.
  • Development process to remove the coating film on the surface processing process to etch and ash the wafer through the opening formed in the coating film, back grinding process
  • a wafer (semiconductor wafer) 201 for cutting out the semiconductor chip 20 is prepared, and a liquid containing a photosensitive adhesive composition is applied thereon. Thereby, a coating film is obtained on the wafer 201 as shown in FIG.
  • the coating method is not particularly limited, and examples thereof include a spin coating method, a spray coating method, an ink jet method, a roll coating method, and a printing method.
  • the liquid (liquid film) containing the applied photosensitive adhesive composition may be heated and dried (prebaked).
  • the heating temperature is preferably about 70 to 160 ° C., more preferably about 80 to 150 ° C.
  • the heating time is appropriately set according to the heating temperature, but is preferably about 5 seconds to 30 minutes, more preferably about 10 seconds to 15 minutes.
  • the liquid containing the photosensitive adhesive composition is prepared by appropriately adding a solvent or the like that can dissolve the liquid to the photosensitive adhesive composition of the present invention. Moreover, it is preferable that the solvent to be used can be removed by volatilization when heated in the process described later.
  • solvents include toluene, xylene, benzene, dimethylformamide, tetrahydrofuran, ethyl cellosolve, ethyl acetate, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol.
  • a solvent containing any of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ⁇ -butyrolactone, and cyclohexanone is particularly preferable because of its high solubility and easy removal by volatilization.
  • Exposure Step the coating film 601a formed on the wafer 201 is subjected to an exposure process on an area (exposure area) having a desired pattern shape. Thereby, a photo-curing reaction occurs in the coating film 601a in the exposure region, and a coating film 601a having a desired pattern shape is obtained.
  • electromagnetic waves and particle beams having various wavelengths are used, and examples thereof include ultraviolet rays such as i-rays, visible rays, lasers, X-rays, and electron beams. Of these, ultraviolet rays or visible rays having a wavelength of about 200 to 700 ⁇ m are preferably used.
  • the exposure process can be performed in, for example, an air atmosphere, an inert gas atmosphere, or a reduced pressure atmosphere.
  • a photomask having a desired pattern shape is provided on the coating film 601a and exposed through the photomask, whereby light is applied to the coating film present in the region where the photomask does not exist (exposure region). causes a curing reaction. Note that when an X-ray or electron beam having high directivity is used for the exposure process, the use of a photomask can be omitted.
  • the exposure amount in the exposure process is appropriately set according to the sensitivity of the photosensitive adhesive composition, but as an example, it is preferably about 30 to 3000 mJ / cm 2 .
  • the coating film 601a subjected to the exposure processing is subjected to development processing. Thereby, the coating film 601a of an unexposed part is removed and a desired pattern shape is obtained.
  • development processing for example, an electrode pad for connecting the bonding wire 70 to the semiconductor chip 20 can be exposed.
  • the coating film on a dicing line can be removed in the dicing process mentioned later.
  • a developer is brought into contact with the coating film 601a subjected to the exposure process. Thereby, the coating film 601a of an unexposed part melt
  • the developer include alkali metal carbonates, alkali metal hydroxides, alkali developers such as tetraammonium hydroxide, organic developers such as dimethylformamide and N-methyl-2-pyrrolidone, and the like. Can be mentioned.
  • an alkaline developer is particularly preferably used as the developer. Note that the alkaline developer has a feature that a load on the environment is small and a residue is hardly generated.
  • examples of the developer supply method include spraying, paddle, dipping, and ultrasonic methods.
  • the coating film 601a has a so-called negative photosensitive property, but the coating film 601a may have a so-called positive photosensitive property.
  • the coating film 601a has positive photosensitivity, the coating film 601a in the exposed portion is dissolved and removed in the developer, thereby forming an opening in the coating film 601a.
  • the physical properties described below can be imparted to the coating film 601a, but the positive type can favorably impart it to the coating film 601a.
  • the wafer 201 provided with the coating film 601a (the portion of the wafer 201 exposed through the opening in the developing step) is subjected to an etching process as necessary. Thereby, when the passivation film (coating) is formed on the surface of the wafer 201, it can be removed and the electrode pad (terminal) for connecting the bonding wire 70 can be exposed.
  • the etching process examples include a plasma etching process (dry etching process) and various wet etching processes.
  • the plasma etching process can be performed under generally known conditions.
  • a fluorine compound gas CF 4 , CHF 3
  • a fluorine compound gas CF 4 , CHF 3
  • an oxygen gas O 2
  • a gas mixture of fluorine compound gas CF 4 , CHF 3
  • argon gas Ar
  • the output is 200 to 2000 W
  • the time is 0.2 to 15 minutes
  • the gas flow rate is 50 It can be performed under conditions of up to 1000 sccm.
  • produced by the etching process can be removed, and the coating-film 601a surface and the electrode pad surface can be cleaned.
  • the adhesive force of the adhesive layer 601 can be increased, and the bonding force of the bonding wire 70 to the electrode pad can be increased.
  • Examples of the ashing process include a wet process using a chemical such as a plasma process.
  • a chemical such as a plasma process.
  • oxygen gas (O 2 ), a mixture gas of oxygen gas (O 2 ) and argon gas (Ar), or the like is used as a treatment gas, the output is 200 to 2000 W, and the time is 0.2 to 15 minutes.
  • the gas flow rate can be 50 to 1000 sccm.
  • the back surface of the wafer 201 is ground (back grinding process). Thereby, the dotted line portion in FIG. 2C is removed, and the thickness of the wafer 201 can be reduced.
  • the thickness of the wafer 201 can be reduced to about 20 to 100 ⁇ m although it depends on the original thickness of the wafer 201.
  • an apparatus called a back grinding wheel is used for this back grinding process.
  • 2B and 2C are views showing a state where the back grind film 90 is attached to the surface of the coating film 601a (the upper surface of FIG. 2A).
  • the back grinding process can be performed by attaching the back grinding film 90 to the surface of the coating film 601a and fixing the wafer 201 in this manner.
  • the wafer 201 on which the coating film 601a is formed is turned upside down with respect to FIG. 2A.
  • a UV peeling type back grind film can be used as the back grind film 90.
  • the back grind film 90 is simply subjected to UV irradiation treatment through the back grind film 90.
  • the adhesive force between 90 and the coating film 601a can be greatly reduced.
  • the back grind film 90 can be smoothly peeled off from the coating film 601a without imposing a large burden on the coating film 601a.
  • the dicing process is performed in a state where the wafer 201 is attached to a dicing die attach film or a dicing film.
  • This dicing die attach film or dicing film is used for fixing the wafer 201 during the dicing process.
  • 2 (d1) and 2 (d2) are diagrams showing an example in which a dicing film 100a is attached to the back surface (upper surface of FIG. 2 (c)) of the wafer 201 whose back surface is ground.
  • 2D1 illustrates a wafer 201 and the like for cutting out the semiconductor chip 20 used for the lowermost layer (the layer closest to the package substrate 30) of the chip stack 200.
  • FIG. 2D2 shows a wafer 201 and the like for cutting out the semiconductor chip 20 used in a layer other than the lowermost layer of the chip stack 200.
  • FIGS. 2 (d1) and 2 (d2) the wafer 201 on which the coating film 601a is formed is turned upside down with respect to FIG. 2 (c).
  • a dicing die attach film 100 which is a laminate of the dicing film 100a and the die attach film 100b, is attached to the back surface of the wafer 201.
  • a dicing film 100 a is attached to the back surface of the wafer 201.
  • the wafer 201 provided with the coating film 601a is subjected to a dicing process.
  • the dicing process is performed so that the dicing blade 110 reaches the dicing film 100a as shown in FIGS. 3 (f1) and 3 (f2).
  • the coating film 601a, the wafer 201 and the die attach film 100b are separated into individual pieces, and as shown in FIG. 3 (g1), the adhesive layer 601, the semiconductor chip 20 and the adhesive are bonded.
  • a piece 21 formed by laminating the layers 101 is cut out.
  • the coating film 601a and the wafer 201 are separated into individual pieces, and as shown in FIG. 3 (g2), the individual pieces formed by laminating the adhesive layer 601 and the semiconductor chip 20 are laminated. 22 is cut out.
  • a plurality of semiconductor chips 20 are cut out by performing a dicing process on one wafer 201 (a joined body of a plurality of semiconductor chips 20).
  • the present invention is not limited to this, and for example, a plurality of semiconductor chips 20 that have been separated into pieces may be used.
  • the dicing process can be omitted.
  • the back grinding process can be omitted.
  • the process order of the back grinding process and the dicing process is not limited to the order described above, and the order may be changed. That is, the back grinding process may be performed after the wafer 201 is subjected to the dicing process.
  • FIGS. 3 (g1) and 3 (g2) are diagrams illustrating an example in which the cut piece 21 and the piece 22 are picked up by the collet 121 of the bonding apparatus 120, respectively.
  • the individual piece 21 is picked up by the collet 121 of the bonding apparatus 120 and is crimped (mounted) on the package substrate 30 as shown in FIG.
  • the back surface of the semiconductor chip 20 and the package substrate 30 are bonded via the adhesive layer 101.
  • the adhesive layer 101 is formed by separating the die attach film 100b.
  • the adhesive layer 101 may be formed of, for example, an uncured product or a semi-cured product (photosensitive adhesive composition that has not been completely cured) of the photosensitive adhesive composition of the present invention.
  • the package substrate 30 also corresponds to a non-joining member that is joined to the semiconductor element 20.
  • the photosensitive adhesive composition of the present invention is used not only for bonding the semiconductor element 20 and the semiconductor element (bonded member) 20 but also for bonding the semiconductor element 20 and the package substrate (bonded member) 30. be able to.
  • a to-be-joined member is not limited to these.
  • the piece 22 is pressure-bonded onto the piece 21 previously mounted.
  • two semiconductor chips 20 can be stacked via the adhesive layer 601.
  • a chip stack 200 in which a large number of semiconductor chips 20 are stacked is obtained.
  • the electrode portions of the semiconductor chip 20 can be exposed by laminating the semiconductor chips 20 while shifting the positions thereof.
  • the adhesive layer 601 is heated. Thereby, the adhesive layer 601 exhibits a sufficient adhesive force, and the semiconductor chips 20 can be firmly bonded to each other.
  • the heating temperature is preferably about 30 to 150 ° C.
  • the crimping load at the time of mounting is about 0.1 to 100 N, and the crimping time is about 0.1 to 10 seconds.
  • each semiconductor chip 20 and the exposed part of the wiring 34 of the package substrate 30 are connected by a bonding wire 70 as shown in FIG.
  • the semiconductor device 10 shown in FIG. 1 is obtained.
  • Molding of the mold part can be performed by, for example, using a transfer molding machine and injecting a sealing material into the mold.
  • the temperature of the mold is about 130 to 250 ° C.
  • the injection pressure is about 3 to 10 MPa
  • the holding time after injection is about 10 seconds to 10 minutes.
  • the molded part and the adhesive layer 601 can be finally cured (completely cured) by heating the molded body as necessary.
  • the heating temperature is preferably about 130 to 250 ° C.
  • the heating time is preferably about 10 minutes to 10 hours.
  • the manufacturing method of the semiconductor device of this invention may have a heating process between the said [3] image development process and a [4] processing process.
  • this heating step the coating film 601a that has been subjected to development processing is heated.
  • a predetermined curing reaction thermalsetting reaction
  • the photosensitive adhesive composition is slightly cured (semi-cured), and the adhesiveness of the coating film 601a is increased.
  • the heating temperature of the coating film 601a is not particularly limited, but is preferably 80 to 170 ° C, and more preferably 120 to 160 ° C.
  • the heating time is appropriately set according to the heating temperature, but is preferably 35 to 120 minutes, and more preferably 40 to 100 minutes. Thereby, mechanical properties such as the elastic modulus of the coating film 601a are optimized, and sufficient resistance to the etching process and the ashing process is imparted to the coating film 601a.
  • the coating film 601a is formed of the photosensitive adhesive composition of the present invention, and the adhesive layer 601 formed from such a coating film 601a exhibits a relatively high solubility in an organic solvent. For this reason, for example, even when it is necessary to remove the coating film 601a after forming the coating film 601a on the wafer 201, the coating film 601a is efficiently dissolved while suppressing the generation of residues (residues). Can be removed. For this reason, the wafer 201 can be used again (reworked) without being wasted. As a result, the process yield of the semiconductor device 10 can be improved.
  • the manufacturing method of the semiconductor device may include a step of irradiating light on the entire surface of the coating film (light irradiation step) in addition to the heating step or instead of the heating step.
  • the adhesive layer 601 for bonding the semiconductor chips 20 to each other is composed of a cured product of the photosensitive adhesive composition of the present invention.
  • Such an adhesive layer 601 is provided with sufficient adhesiveness and stress relaxation properties despite the single layer structure. Therefore, it is possible to obtain a highly reliable chip stack 200 in which stress concentration between layers caused by a difference in thermal expansion and the like is reduced while preventing the entire thickness of the chip stack 200 from being significantly increased. . As a result, a low-profile and highly reliable semiconductor device 10 can be obtained.
  • Such a semiconductor device 10 has a very small internal volume, such as a mobile device, and is particularly useful in an electronic device that is used while being carried. That is, such a semiconductor device 10 is useful in that it contributes to the reduction in size, thickness, and weight of the electronic device and that the function of the semiconductor device 10 is hardly impaired even when the electronic device is dropped or swung. It is.
  • the elastic modulus at 25 ° C. of the cured photosensitive adhesive composition that is, the adhesive layer 601 is set to 2.0 to 3.5 GPa.
  • the elastic modulus at 25 ° C. of the photosensitive adhesive composition before curing is 70 to 120% of the elastic modulus at 25 ° C. of the photosensitive adhesive composition after curing.
  • the adhesive strength of the photosensitive adhesive composition before being subjected to etching treatment and ashing treatment to the semiconductor chip 20 at 25 ° C. is 20.0 to 200.0 N.
  • a film is formed on the semiconductor chip 20 having a size of 4 mm ⁇ 4 mm in plan view, and the film is not cured (completely cured) without being cured or semi-cured.
  • the adhesion strength of the film to the semiconductor chip 20 at 25 ° C. is 20.0 to 200.0 N It is.
  • this adhesive force is converted per unit area of the size of the semiconductor chip 20 in plan view, it is 1.25 to 12.5 MPa (N / mm 2 ).
  • the elastic modulus at 25 ° C. of the photosensitive adhesive composition before curing is within a predetermined range with respect to the elastic modulus at 25 ° C. of the photosensitive adhesive composition after curing, for example, curing
  • the risk of the previous photosensitive adhesive composition being significantly deformed or flowing out of the wafer 201 is reduced. For this reason, it is possible to improve the alignment accuracy when the semiconductor chips 20 are stacked.
  • the amount of change in elastic modulus before and after curing is relatively small, the amount of shrinkage associated with exposure can also be reduced. As a result, it is possible to reduce stress generated at the interface between the adhesive layer 601 and the semiconductor chip 20 along with curing shrinkage. From this viewpoint, it contributes to improving the reliability of the chip stack 200.
  • the pre-curing photosensitive adhesive composition that has been subjected to the etching process and the ashing process has sufficient adhesion to the semiconductor chip 20 required for die bonding.
  • the adhesive layer 601 reliably fixes the semiconductor chips 20 to each other and contributes to improving the reliability of the chip stack 200.
  • the adhesive layer 601 combines the element protection function (buffer coating function) of the buffer coating film and the bonding function (die bonding function) of the die bonding film with one layer. For this reason, it is possible to form the chip stacked body 200 without reducing the reliability of the chip stacked body 200, and it is possible to make the chip stacked body 200 thinner than the conventional case where two layers are used. Further, as the chip stack 200 is made thinner, the volume of the mold part 50 can be reduced and the bonding wire 70 can be shortened, thereby contributing to weight reduction and cost reduction.
  • the elastic modulus at 25 ° C. before curing is 2.0 to 3.5 GPa as described above, preferably 2.2 to 3.2 GPa, more preferably 2.4 to 3.0 GPa.
  • the elasticity modulus of the photosensitive adhesive composition after hardening is less than the said lower limit, there exists a possibility that the adhesive force of the contact bonding layer 601 may fall and the interface with the semiconductor chip 20 may peel. Further, when the mold part 50 contains a filler, the filler may penetrate the adhesive layer 601 and adversely affect the semiconductor chip 20.
  • the elastic modulus of the photosensitive adhesive composition after curing exceeds the upper limit value, the flexibility of the adhesive layer 601 is lowered, so that the stress relaxation property is lowered.
  • the residual stress caused by the stacking of the semiconductor chips 20 and the local concentration of the thermal stress due to the thermal expansion difference between the semiconductor chip 20 and the adhesive layer 601 cannot be reduced, and the semiconductor chip 20 is cracked. Or may be peeled between the semiconductor chip 20 and the adhesive layer 601.
  • the elastic modulus of the cured photosensitive adhesive composition is, for example, a measurement temperature of 25 ° C., a load of 2 mN, a holding time of 1 second using an ultra-micro hardness meter ENT-1000 (manufactured by Elionix). Using an indenter (triangular pyramid, opposite ridge angle 115 °), it can be determined by measuring in accordance with ISO14577.
  • the elastic modulus at 25 ° C. of the photosensitive adhesive composition before curing is 70 to 120% of the elastic modulus at 25 ° C. of the photosensitive adhesive composition after curing, as described above. Preferably it is 75 to 115%, more preferably 80 to 110%.
  • the elasticity modulus of the photosensitive adhesive composition before hardening is less than the said lower limit, the adhesiveness of the photosensitive adhesive composition increases, but the film of the photosensitive adhesive composition is easily deformed. As a result, for example, when the semiconductor chip 20 is temporarily arranged through this film, the position may be easily displaced, or the photosensitive adhesive composition may flow out of the wafer 201.
  • the elastic modulus of the photosensitive adhesive composition before curing exceeds the upper limit value, the tackiness is lowered, and it may be difficult to temporarily arrange the semiconductor chip 20.
  • the elasticity modulus of the photosensitive adhesive composition before hardening can also be measured similarly to the elasticity modulus of the photosensitive adhesive composition after hardening.
  • the adhesive force at 25 ° C. of the photosensitive adhesive composition before being subjected to the etching treatment and the ashing treatment to the semiconductor chip 20 is 20 to 200 N (1.25 to 12.5 MPa) as described above. However, it is preferably 30 to 180 N (1.875 to 11.25 MPa), and more preferably 40 to 160 N (2.5 to 10 MPa).
  • the adhesive force is lower than the lower limit value, depending on conditions at the time of manufacturing the semiconductor device 10, there is a possibility that the reliability of the semiconductor device 10 is lowered due to the release of the bonding between the semiconductor chips 20.
  • the adhesive strength exceeds the upper limit no structural problem occurs, but no further increase in effect can be expected.
  • the adhesive strength of the photosensitive adhesive composition before being subjected to etching treatment and ashing treatment to the semiconductor chip 20 can be measured as follows. First, the semiconductor chips 20 are bonded to each other through the uncured photosensitive adhesive composition subjected to the etching process and the ashing process to obtain a semiconductor chip bonded body. Thereafter, the universal bond tester Dage4000 (manufactured by Daisy Japan Co., Ltd.) is used to determine the die shear strength of the bonded semiconductor chip as the adhesive strength to the semiconductor chip 20.
  • the die shear strength is obtained as strength when one semiconductor chip 20 is pushed in the horizontal direction (in the in-plane direction of the semiconductor chip) with a shear tool from the side (side surface) of the bonded semiconductor chip body and the joint surface between the chips is broken. It is done.
  • the etching process is, for example, a process of removing a passivation film on the surface of a semiconductor chip and exposing an electrode pad for connecting a bonding wire.
  • a mixed gas of fluorine compound gas (CF 4 ), argon gas (Ar), and oxygen gas (O 2 ) is used as the gas, the output is 2500 W, the time is 6 minutes, and the CF 4 flow rate / Ar flow rate / O.
  • the etching process performed on the conditions which 2 flow volume is 200 sccm / 200 sccm / 50 sccm is mentioned.
  • the ashing process is, for example, a process of removing a processing residue generated by an etching process and cleaning the surface of the adhesive layer and the electrode pad.
  • plasma treatment is performed using a mixed gas of oxygen gas (O 2 ) and Ar, the output is 600 W, the time is 12 minutes, and the O 2 flow rate / Ar flow rate is 50 sccm / 150 sccm.
  • Such etching process and ashing process may promote the deterioration of the organic material. For this reason, when it is a coating film (adhesion layer) with low etching process tolerance and ashing process tolerance, there exists a possibility that semiconductor chip 20 cannot fully be adhere
  • the coating film 601a (adhesive layer 601) formed by using the photosensitive adhesive composition of the present invention has sufficient etching processing resistance and ashing processing resistance. For this reason, even after passing through such etching treatment and ashing treatment, a decrease in the adhesive strength of the coating film 601a is suppressed, and as a result, the adhesive strength as described above is exhibited. Therefore, since the photosensitive adhesive composition of the present invention does not need to consider a decrease in adhesiveness in various processes in the semiconductor manufacturing process, the manufacturing process of the semiconductor device 10 can be simplified and the cost can be easily reduced. This is useful in that it can be achieved.
  • the rate of change of the elastic modulus of the photosensitive adhesive composition before and after the treatment step is preferably within a certain range. Therefore, it is preferable to appropriately set the heating conditions in the heating step that is considered to affect the resistance to the processing step (etching resistance and ashing resistance) so that the rate of change is within a certain range.
  • the elastic modulus at 25 ° C. after the heating step and before the processing step of the photosensitive adhesive composition is X [GPa]
  • the elastic modulus at 25 ° C. after the processing step is Y [GPa].
  • X and Y preferably satisfy the relationship of 0.7 ⁇ X / Y ⁇ 1.5, and more preferably satisfy the relationship of 0.8 ⁇ X / Y ⁇ 1.3. Since the rate of change in elastic modulus before and after the treatment process satisfies the above relationship, the coating film 601a formed of the photosensitive adhesive composition has sufficient mechanical characteristics to maintain the patterned shape. At the same time, it has sufficient adhesiveness to bond the semiconductor chips 20 together.
  • the coating film 601a in the processing step in which the etching process and the ashing process are performed, the deterioration of the coating film 601a is promoted, but when the rate of change in elastic modulus before and after the processing process satisfies the above relationship, the coating film 601a is In addition, the adhesive layer 601 functions sufficiently in the mounting process while sufficiently retaining the patterned shape. For this reason, when the change rate of the elastic modulus before and after the treatment process satisfies the above relationship, the coating film 601a composed of such a photosensitive adhesive composition has a function as an etching mask and an adhesive layer 601. Both functions can be achieved.
  • the minimum melt viscosity at 100 to 200 ° C. of the photosensitive adhesive composition before curing is set to 20 to 500 Pa ⁇ s. Since such a photosensitive adhesive composition is excellent in wettability with respect to the semiconductor chip 20, voids and the like hardly occur in the adhesive layer 601. Therefore, a uniform adhesive layer 601 with little variation in physical properties can be formed. As a result, when the semiconductor chips 20 are bonded to each other via the adhesive layer 601, local concentration of stress is less likely to occur, generation of cracks in the semiconductor chip 20, occurrence of peeling between the semiconductor chip 20 and the adhesive layer 601, and the like. Can be suppressed. In addition, the minimum melt viscosity of the photosensitive adhesive composition before curing can be measured with a rheometer.
  • the minimum melt viscosity of the photosensitive adhesive composition before curing is preferably 25 to 400 Pa ⁇ s, more preferably 30 to 300 Pa ⁇ s.
  • the tackiness can be reduced by subjecting it to UV irradiation treatment. Therefore, the tackiness (adhesive strength) of the photosensitive adhesive composition before curing can be controlled by the presence or absence of UV irradiation treatment.
  • the adhesive strength of the photosensitive adhesive composition before curing to the back grind film 90 will be described.
  • the coating film 601a is formed on the wafer 201 using the photosensitive adhesive composition of the present invention.
  • the etching process and the ashing process described above are performed on the wafer 201 including the uncured or semi-cured coating film 601a (photosensitive adhesive composition before curing) without curing (completely curing) the coating film 601a.
  • a UV peeling type back grind film 90 is stuck on the coating film 601a, and the adhesive strength of the back grind film 90 to the coating film 601a at 25 ° C. is measured.
  • Such adhesive strength is preferably 3.0 N / 25 mm or more.
  • Such a photosensitive adhesive composition of the present invention exhibits sufficient adhesion to the back grind film 90 even after being subjected to a treatment that promotes deterioration of the organic material such as an etching treatment or an ashing treatment. Can do. For this reason, for example, when the back grinding process is performed on the wafer 201 on which the coating film 601a of the photosensitive adhesive composition of the present invention is formed, the wafer 201 can be securely fixed, and the accuracy of the back grinding process is further increased. be able to.
  • the adhesive strength is more preferably 3.5 N / 25 mm or more and 10.0 N / 25 mm or less.
  • the adhesive strength can be measured as follows. First, a UV peeling type back grind film 90 (25 mm in width and 75 mm in length) is bonded so that the adhesive surface is in contact with the coating film 601a after the etching process and the ashing process. Next, the measurement temperature is set to 25 ° C., the peeling speed is set to 10.0 ⁇ 0.2 mm / s, and one end in the longitudinal direction of the back grind film 90 is pulled so that the peeling angle is 180 °, The back grind film 90 is peeled off from the coating film 601a of the photosensitive adhesive composition of the present invention. The adhesive force can be determined by measuring the average value of the load required for peeling at this time (180 ° peeling adhesive strength, unit: N / 25 mm, JIS Z 0237 compliant).
  • the adhesive strength at 50 ° C. to the back grind film 90 of the photosensitive adhesive composition before being cured after being subjected to the UV irradiation treatment after being subjected to the etching treatment and the ashing treatment back after the UV irradiation treatment.
  • the adhesive force to the grind film 90 is preferably 0.5 N / 25 mm or less. Thereby, the adhesive force with respect to the back grind film 90 after UV irradiation processing can be made small enough. Therefore, for example, after the back grind treatment, when the back grind film 90 is peeled off from the coating film 601a of the photosensitive adhesive composition of the present invention, the back grind film 90 is smoothly peeled without exerting a large load on the coating film 601a. Can do.
  • the back grind film 90 can be peeled without impairing the adhesion between the coating film 601a and the semiconductor chip 20.
  • the photosensitive adhesive composition of the present invention adheres to the dicing blade 110 in the dicing step, or the photosensitive property of the present invention in the mounting step. It is possible to suppress the adhesive composition from adhering to the collet 121. As a result, it is possible to suppress the occurrence of dicing failure and pickup failure.
  • the adhesive force with respect to the back grind film 90 after UV irradiation treatment is more preferably 0.05 N / 25 mm or more and 0.40 N / 25 mm or less.
  • the coating film 601a is irradiated with light having a wavelength of 365 nm through the back grind film 90 so that the integrated light amount is 600 mJ / cm 2 .
  • the UV peeling type back grind film 90 is made of an acrylic resin.
  • the measurement of the adhesive force with respect to the back grind film 90 after UV irradiation processing is the adhesive force at 25 degreeC with respect to the back grind film 90 of the photosensitive adhesive composition before hardening after using for an etching process and an ashing process.
  • the same measurement method as described above can be used.
  • a photosensitive adhesive composition will not be specifically limited if it is a composition which can change the solubility with respect to aqueous alkali solution and / or an organic solvent by light irradiation, and can express adhesiveness.
  • the photosensitive adhesive composition of the present embodiment includes (A) an alkali-soluble resin, (B) a photoacid generator, (C) an epoxy compound, and (D) a phenol compound.
  • a material which comprises the photosensitive adhesive composition which concerns on this embodiment is demonstrated in detail.
  • the alkali-soluble resin is a material that becomes a base material of the adhesive layer 601.
  • the photosensitive adhesive composition can enhance the adhesive force (adhesive force) of the adhesive layer 601 to the semiconductor chip 20 by including (A) an alkali-soluble resin. Therefore, the semiconductor chips 20 can be more firmly bonded to each other depending on the adhesive layer 601.
  • the photosensitive adhesive composition contains (A) an alkali-soluble resin, the coating film 601a can be provided with solubility in an alkali developer. For this reason, an alkaline developer having a small environmental load can be used, and the environmental load in the development process can be reduced.
  • the alkali-soluble resin examples include phenolic resins, acrylic resins, cyclic olefin resins, polyamide resins, polyimide resins, polyvinylphenol resins, etc. Species or a combination of two or more can be used. Among these, (A) the alkali-soluble resin is particularly preferably a cyclic olefin resin.
  • the cyclic olefin-based resin examples include norbornene-based resins and benzocyclobutene-based resins. Among these, norbornene-based resins are preferable as the cyclic olefin-based resin.
  • the contact bonding layer 601 can improve the adhesive strength of the semiconductor chips 20 by containing norbornene-type resin.
  • the cyclic olefin-based resin preferably has at least one repeating unit having an acidic group (first repeating unit).
  • the first repeating unit includes a structure derived from a cyclic olefin (cyclic olefin monomer) as a main skeleton and a substituent having an acidic group bonded to the structure.
  • cyclic olefins monocyclic compounds such as cyclohexene and cyclooctene, norbornene, norbornadiene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, tricyclopentadiene, dihydrotricyclopentadiene, tetracyclopentadiene, Examples include structures derived from polycyclic compounds such as dihydrotetracyclopentadiene.
  • the structure derived from cyclic olefin is particularly preferably a structure derived from norbornene from the viewpoints of heat resistance of the photosensitive adhesive composition and flexibility of the cured photosensitive adhesive composition. .
  • substituent having an acidic group examples include a substituent having a carboxyl group, a phenolic hydroxyl group, —C (OH) — (CF 3 ) 2 , —N (H) —S (O) 2 —CF 3, and the like.
  • a substituent having either a carboxyl group or —C (OH) — (CF 3 ) 2 is particularly preferable.
  • cyclic olefin resin contains the substituent which has such an acidic group, the solubility with respect to the alkaline developing solution of the photosensitive adhesive composition can be improved. For this reason, development with an alkaline developer is possible in the manufacture of a semiconductor device. Moreover, the undissolved residue of the photosensitive adhesive composition after development can be reduced, and the patterning property during development can be further improved.
  • the first repeating unit is particularly preferably at least one of the following formula (2) and the following formula (3).
  • the cyclic olefin-based resin contains such a repeating unit, the adhesiveness of the adhesive layer 601 to the semiconductor chip 20 can be improved, and a photosensitive adhesive composition that can be developed with an alkali developer can be obtained. it can.
  • x and y are each preferably an integer of 0 or more and 10 or less, and particularly preferably an integer of 1 or more and 5 or less. Thereby, it is possible to obtain the adhesive layer 601 that is superior in the bonding strength between the semiconductor chips 20.
  • the cyclic olefin-based resin preferably has a repeating unit (first repeating unit) having at least one acidic group, but more preferably has a repeating unit having two or more different acidic groups.
  • the content of the first repeating unit in the cyclic olefin-based resin can be determined in consideration of the solubility of the photosensitive adhesive composition in an alkaline developer, and is, for example, 10 to 80 mol%. It is preferable that it is 20 to 70 mol%. If the content of the first repeating unit is less than the lower limit, it may be difficult to sufficiently develop the solubility of the photosensitive adhesive composition in an alkaline developer. Moreover, when the content rate of a 1st repeating unit exceeds the said upper limit, depending on the kind of 1st repeating unit, there exists a possibility that the characteristic of materials other than cyclic olefin resin cannot fully be expressed.
  • the acidic group in the cyclic olefin resin is preferably 0.001 to 0.01 mol per 1 g of the polymer.
  • the amount is more preferably 0.0015 to 0.006 mol.
  • the cyclic olefin resin further has a second repeating unit different from the first repeating unit.
  • the second repeating unit includes a structure derived from a cyclic olefin as a main skeleton and a substituent that is bonded to the structure and is different from the substituent of the first repeating unit.
  • the main skeleton of the second repeating unit As the main skeleton of the second repeating unit, the structure exemplified in the first repeating unit described above can be used. Among these, the main skeleton of the second repeating unit is a structure derived from norbornene from the viewpoint of the heat resistance of the photosensitive adhesive composition and the flexibility of the photosensitive adhesive composition after curing. Particularly preferred.
  • the main skeletons of the first and second repeating units may be different from each other, but are preferably the same.
  • the main skeletons of the first and second repeating units are preferably structures derived from norbornene.
  • the substituent of the second repeating unit preferably has 2 to 30 carbon atoms, and more preferably 4 to 15 carbon atoms.
  • the elastic modulus of the photosensitive adhesive composition after curing can be set to an appropriate value.
  • the substituent of the second repeating unit may be a cyclic structure, a branched structure, or the like, but is preferably a linear structure. Thereby, the elasticity modulus of the photosensitive adhesive composition after hardening can be made into an appropriate value.
  • linear substituent having 2 to 30 carbon atoms examples include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, and a group having an alkyl ether structure.
  • the linear substituent having 2 to 30 carbon atoms is particularly preferably a group having an alkyl ether structure.
  • the group having an alkyl ether structure is particularly preferably a group represented by the following formula (1).
  • z is preferably an integer of 1 or more and 10 or less, and more preferably an integer of 2 or more and 6 or less.
  • the second repeating unit is particularly preferably the following formula (4).
  • the cyclic olefin-based resin has the second repeating unit represented by the following formula (4) in addition to the first repeating unit described above, so that the photosensitive adhesive composition is dissolved in the alkaline aqueous solution by the first repeating unit.
  • the function of sufficiently exhibiting the property and the function of setting the elastic modulus of the photosensitive adhesive composition after curing to an appropriate value can be achieved. For this reason, the adhesive layer 601 is prevented from being damaged by an external impact.
  • z is preferably an integer of 1 to 10, more preferably an integer of 2 to 5.
  • the content of the second repeating unit in the cyclic olefin-based resin is preferably, for example, 20 to 60 mol%, and preferably 25 to 50 mol%. Is more preferable.
  • the content rate of the second repeating unit is less than the lower limit, it is difficult to adjust the elastic modulus of the photosensitive adhesive composition after curing to a desired value depending on the type of the second repeating unit. There is a case.
  • the content rate of a 2nd repeating unit exceeds the said upper limit, depending on the kind of 2nd repeating unit, the characteristic derived from other materials other than cyclic olefin resin may not fully be expressed.
  • a cyclic olefin resin represented by the following formula (5) is preferably used.
  • l, m, and n are integers of 1 or more and 100 or less.
  • x is preferably an integer of 0 or more and 10 or less
  • y is preferably an integer of 0 or more and 10 or less
  • z is an integer of 1 or more and 10 or less. preferable.
  • the degree of polymerization of the repeating unit (second repeating unit) having a group containing an alkyl ether structure with respect to the degree of polymerization of the repeating unit having acidic group (first repeating unit) is preferably from 0.3 to 2.0, more preferably from 0.4 to 1.5.
  • the weight average molecular weight of the cyclic olefin resin is preferably 5,000 to 500,000, more preferably 7,000 to 200,000, and further preferably 8,000 to 100,000. preferable. Thereby, the adhesive layer 601 provided with sufficient adhesiveness can be obtained.
  • the weight average molecular weight can be measured by gel permeation chromatography (GPC) using a standard cyclic olefin resin (polynorbornene) in accordance with ASTM DDS 3536-91 ().
  • GPC gel permeation chromatography
  • Such a cyclic olefin-based resin is obtained by polymerizing a cyclic olefin monomer (hereinafter sometimes simply referred to as “monomer”).
  • addition polymers obtained by the addition polymerization method include (1) addition (co) polymers of norbornene monomers obtained by addition (co) polymerization of norbornene monomers, and (2) norbornene monomers and ethylene. And addition copolymers with ⁇ -olefins, (3) addition copolymers of norbornene type monomers with non-conjugated dienes, and other monomers as required. Addition (co) polymers are also preferred because they are rich in transparency, heat resistance and flexibility.
  • Examples of the ring-opening polymer obtained by the ring-opening polymerization method include (4) a ring-opening (co) polymer of a norbornene-type monomer, and a resin obtained by hydrogenating the (co) polymer, if necessary, ( 5) Ring-opening copolymer of norbornene-type monomer and ethylene or ⁇ -olefin, and a resin obtained by hydrogenating the (co) polymer if necessary, (6) norbornene-type monomer and non-conjugated diene, or others And a resin obtained by hydrogenating the (co) polymer if necessary.
  • the norbornene-based resin includes (1) an addition (co) polymer obtained by addition (co) polymerization of a norbornene type monomer, (4) a ring-opening (co) polymer of a norbornene type monomer, and Accordingly, a resin obtained by hydrogenating the (co) polymer is preferable.
  • Examples of monomers (cyclic olefin monomers) for obtaining a cyclic olefin resin by such a polymerization method include, for example, monocyclic compounds such as cyclohexene and cyclooctene, norbornene, norbornadiene, dicyclopentadiene, dihydrodicyclopentadiene, and tetracyclohexane. And monomers having a substituent bonded to a polycyclic compound such as dodecene, tricyclopentadiene, dihydrotricyclopentadiene, tetracyclopentadiene, and dihydrotetracyclopentadiene.
  • a norbornene type monomer represented by the following formula (6) is particularly preferable.
  • n is an integer from 0 to 5.
  • R 1 to R 4 each independently contain hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a substituent having an alkyl ether structure, a substituent containing an ester group, or a ketone group Substituents, substituents containing ether groups, carboxyl groups, phenolic hydroxyl groups, acidic groups such as —C (OH) — (CF 3 ) 2 , —N (H) —S (O) 2 —CF 3 Any of the groups to be used may be used.
  • R 1 to R 4 may be different among the repeating monomers, but at least one of R 1 to R 4 of all repeating units preferably has an acidic group.
  • the number of carbon atoms in R 1 to R 4 is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 12.
  • alkyl group in the formula (6) include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, cyclopentyl, cyclohexyl, cyclooctyl group and the like.
  • alkenyl group include vinyl, allyl, butynyl, and cyclohexenyl groups.
  • alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl group and the like.
  • aryl group examples include phenyl, naphthyl, and anthracenyl groups.
  • aralkyl group include benzyl and phenethyl groups.
  • group containing an acidic group examples include a carboxyl group, a phenolic hydroxyl group, —C (OH) — (CF 3 ) 2 , and —N (H) —S (O) 2 —CF 3 .
  • the structure is not particularly limited as long as the substituent has these groups.
  • the substituent containing an ether group includes a functional group containing a cyclic ether such as an epoxy group or an oxetane group.
  • the group having an alkyl ether structure is not particularly limited as long as it is a substituent having an alkyl ether structure, but a group having a group represented by the following formula (1) is preferable.
  • z is preferably an integer of 1 or more and 10 or less, and more preferably an integer of 2 or more and 6 or less.
  • the addition polymer of the cyclic olefin resin is obtained by coordination polymerization using a metal catalyst or radical polymerization.
  • a metal catalyst or radical polymerization in coordination polymerization, a polymer is obtained by polymerizing a monomer in a solution in the presence of a transition metal catalyst (NiCOLE R. GROVE et al. Journal of Polymer Science: part B, Polymer Physics, Vol. 37, 3003-3010 (1999)).
  • metal catalysts for coordination polymerization include (toluene) bis (perfluorophenyl) nickel, (mesylene) bis (perfluorophenyl) nickel, (benzene) bis (perfluorophenyl) nickel, bis (tetrahydro) bis (Known metal catalysts such as perfluorophenyl) nickel, bis (ethyl acetate) bis (perfluorophenyl) nickel, and bis (dioxane) bis (perfluorophenyl) nickel may be mentioned.
  • radical polymerization monomers are reacted in a solution set at a temperature of 50 ° C. to 150 ° C. in the presence of a radical initiator.
  • the radical initiator include azobisisobutyronitrile (AIBN), benzoyl peroxide, lauryl peroxide, azobisisocapronitrile, azobisisoleronitrile, and t-butyl hydrogen peroxide.
  • the ring-opening polymer of the cyclic olefin resin is obtained by a known ring-opening polymerization method. First, using a titanium or tungsten compound as a catalyst, at least one norbornene-type monomer is ring-opened (co) polymerized to produce a ring-opened (co) polymer. Next, if necessary, a carbon-carbon double bond in the ring-opening (co) polymer is hydrogenated by a conventional hydrogenation method to produce a thermoplastic saturated norbornene resin. As a result, a ring-opened polymer of the cyclic olefin resin is obtained.
  • the cyclic olefin-based resin can be obtained by directly polymerizing a monomer having an acidic group by the above method.
  • the catalyst or the like may be deactivated by the acidic group of the monomer, and the polymerization may not proceed appropriately.
  • a cyclic olefin-based resin having an acidic group can be obtained by introducing a protective group into the acidic group, polymerizing, and deprotecting the polymer after production.
  • a technique may be adopted in which a functional group capable of chemically reacting with an acidic group is introduced into a monomer having no acidic group, and the functional group is converted into an acidic group by a polymer reaction after polymer synthesis.
  • the cyclic olefin-based resin uses a cyclic olefin monomer in which a hydrogen atom capable of ionizing an acidic group in the cyclic olefin monomer is substituted with another structure, and after polymerizing the cyclic olefin monomer, the cyclic olefin resin is deprotected.
  • a hydrogen atom capable of ionizing an acidic group in the cyclic olefin monomer is substituted with another structure, and after polymerizing the cyclic olefin monomer, the cyclic olefin resin is deprotected.
  • Specific examples of functional groups that can be substituted with hydrogen atoms at this time include tertiary butyl groups, tertiary butoxycarbonyl groups, tetrahydropyran-2-yl groups, trialkylsilyl groups such as trimethylsilyl groups, and methoxymethyl
  • a method for obtaining a cyclic olefin resin containing a repeating unit having an acidic group from a cyclic olefin resin having no acidic group will be described.
  • a cyclic olefin-based resin having no acidic group is mixed with an acidic group-containing compound in the presence of a radical initiator and heated to cause a reaction (polymer reaction).
  • a reaction polymer reaction
  • the acidic group-containing compound examples include acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, 2-hydroxyethyl (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, endocis-bicyclo [2.2.1] hept- Unsaturated carboxylic acid compounds such as 5-ene-2,3-dicarboxylic acid, methyl-endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid, or esters or amides thereof, Alternatively, unsaturated carboxylic acid anhydrides such as maleic anhydride, chloromaleic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride, citraconic anhydride and the like can be mentioned.
  • unsaturated carboxylic acid anhydrides such as maleic anhydride, chloromaleic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride
  • Monomers for obtaining a cyclic olefin-based resin are described in, for example, JP-A-2007-78820.
  • a cyclic olefin-based resin having an acidic group specifically, as a monomer having an acidic group or a monomer having a functional group that is deprotected to become an acidic group, bicyclo [2.2. 1] hept-2-ene-5-carboxylic acid, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene-8-carboxylic acid, 8-methyltetracyclo [4.4.0.1 2,5 .
  • Examples of the monomer having an alkyl group include 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, 5-butyl-2-norbornene, 5-pentyl-2-norbornene, 5- Examples include hexyl-2-norbornene, 5-heptyl-2-norbornene, 5-octyl-2-norbornene, 5-nonyl-2-norbornene, and 5-decyl-2-norbornene.
  • Examples of the monomer having an alkenyl group include 5-allyl-2-norbornene, 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, and 5- (2-propenyl) -2.
  • Examples of the monomer having an alkynyl group include 5-ethynyl-2-norbornene.
  • Examples of the monomer having an alkoxysilyl group include dimethylbis ((5-norbornen-2-yl) methoxy)) silane.
  • Examples of the monomer having a silyl group include 1,1,3,3,5,5-hexamethyl-1,5-dimethylbis ((2- (5-norbornen-2-yl) ethyl) trisiloxane.
  • Examples of the monomer having an aryl group include 5-phenyl-2-norbornene, 5-naphthyl-2-norbornene, 5-pentafluorophenyl-2-norbornene, etc.
  • the monomer having an aralkyl group includes 5-benzyl-2. -Norbornene, 5-phenethyl-2-norbornene, 5-pentafluorophenylmethane-2-norbornene, 5- (2-pentafluorophenylethyl) -2-norbornene, 5- (3-pentafluorophenylpropyl) -2- Norbornene, etc.
  • Examples of the monomer having an epoxy group include 5-[(2,3-epoxypropoxy) methyl] -2-norbornene.
  • Examples of the monomer having a tetracyclo ring include 8,9-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 2,5 . 0 1,6 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 2,5 .
  • suitable polymerization solvents for the polymerization system described above include hydrocarbon solvents and aromatic solvents.
  • hydrocarbon solvent include pentane, hexane, heptane, and cyclohexane, but are not limited thereto.
  • aromatic solvent include, but are not limited to, benzene, toluene, xylene and mesitylene.
  • diethyl ether, tetrahydrofuran, ethyl acetate, ester, lactone, ketone, amide can also be used. These can be used alone as a polymerization solvent, but can also be used as a mixture.
  • the molecular weight of the cyclic olefin resin can be controlled by changing the ratio of the initiator to the monomer or changing the polymerization time.
  • the molecular weight can be controlled by using a chain transfer catalyst.
  • ⁇ -olefins such as ethylene, propylene, 1-hexane, 1-decene, 4-methyl-1-pentene are suitable for controlling the molecular weight.
  • the glass transition temperature of the cyclic olefin resin is preferably 100 to 250 ° C.
  • the glass transition temperature of cyclic olefin resin can be calculated
  • the (A) alkali-soluble resin other than the cyclic olefin resin is also synthesized so as to satisfy the same conditions as described for the cyclic olefin resin, thereby obtaining the same effect as described above.
  • the photoacid generator is a negative-type light capable of accelerating a reaction of crosslinking (A) an alkali-soluble resin (particularly a cyclic olefin resin) by (C) an epoxy compound described later by energy ray irradiation. It has a function as an acid generator.
  • the photoacid generator (B) generates a positive photoacid which generates an acid (for example, a carboxyl group) by a photoreaction at the time of exposure by irradiation with actinic rays and increases the solubility of the exposed portion in an alkaline developer. It may have a function as an agent.
  • Examples of (B) photoacid generators include onium salts, halogenated organic compounds, quinonediazide compounds, ⁇ , ⁇ -bis (sulfonyl) diazomethane compounds, ⁇ -carbonyl- ⁇ -sulfonyl-diazomethane compounds, sulfone compounds, and organic compounds.
  • An acid ester compound, an organic acid amide compound, an organic acid imide compound, etc. are mentioned, Among these, it can use 1 type or in combination of 2 or more types. Among these, it is particularly preferable to use a quinonediazide compound as the photoacid generator (B).
  • Examples of the quinonediazide compound include compounds having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure. These are known substances from U.S. Pat. Nos. 2,729,975, 2,797,213 and 3,669,658.
  • the (B) photoacid generator is 1,2-naphthoquinone-2-diazide-5-sulfonic acid or an ester compound of 1,2-naphthoquinone-2-diazide-4-sulfonic acid and a phenol compound. Is more preferable.
  • the content of the (B) photoacid generator is not particularly limited, but is preferably 1 to 50 parts by mass with respect to 100 parts by mass of (A) the alkali-soluble resin (particularly the cyclic olefin resin). More preferred is part by mass. (B) When content of a photo-acid generator is less than the said lower limit, the exposure of a photosensitive adhesive composition and a development characteristic may fall.
  • the content of (B) the photoacid generator exceeds the above upper limit, the content of (A) the alkali-soluble resin is relatively reduced, so that the portion to be dissolved and removed by the alkali developer (positive type) If so, the solubility of the exposed portion) in the alkali developer is lowered, and depending on the type of the (A) alkali-soluble resin, the sensitivity of the photosensitive adhesive composition to light tends to be lowered, which is not preferable.
  • Epoxy compound has a function which bridge
  • alkali-soluble resin especially cyclic olefin resin.
  • the epoxy compound may be either an aromatic epoxy compound having an aromatic ring in the molecule or an aliphatic epoxy compound having no aromatic ring in the molecule.
  • the (C) epoxy compound is more preferably an aliphatic epoxy compound.
  • the (C) epoxy compound may have a cyclic structure, but preferably has a branched structure or a linear structure, and more preferably has a branched structure.
  • the photosensitive adhesive composition contains (C) an epoxy compound having a branched structure, so that the crosslinking density of the (A) alkali-soluble resin (especially cyclic olefin resin) in the photosensitive adhesive composition is moderate. While being able to make it a small value, the softness
  • the (C) epoxy compound preferably contains two or more glycidyl groups in the molecule, and more preferably contains 3 or more and 9 or less glycidyl groups in the molecule.
  • Examples of such (C) epoxy compounds include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether.
  • (C) epoxy compounds include trimethylolpropane triglycidyl ether, 1,6-hexanediol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, hydrogenated Bisphenol A diglycidyl ether is particularly preferred.
  • (A) alkali-soluble resin (especially cyclic olefin resin) in the photosensitive adhesive composition can be accelerated
  • the content of the epoxy compound (C) is not particularly limited, but is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin (particularly the cyclic olefin resin), and 5 to 50 parts by mass. It is more preferable that (C) If the content of the epoxy compound is less than the lower limit, physical properties of the cured photosensitive adhesive composition may be poor. (C) When content of an epoxy compound exceeds the said upper limit, the viscosity of a photosensitive adhesive composition may become high more than necessary.
  • (D) A phenol compound has a function which improves the sensitivity with respect to the light of a photosensitive adhesive composition. For this reason, the undissolved residue of the photosensitive adhesive composition at the time of development can be prevented. Moreover, the (D) phenol compound can improve the remaining film rate of the coating film 601a by interacting with the (B) photoacid generator. For this reason, the patterning property during development can be improved.
  • the phenol compound (D) preferably has a hydroxyl group equivalent of 60 to 150 g / eq, more preferably a hydroxyl group equivalent of 70 to 140 g / eq, and a hydroxyl group equivalent of 75 to 135 g. More preferred is / eq.
  • the hydroxyl equivalent is within the above range, the photosensitive adhesive composition becomes soluble in an alkaline aqueous solution used during development.
  • the hydroxyl equivalent is less than the lower limit and a positive type (B) photoacid generator is used, there is a possibility that even the coating film 601a in the unexposed area is dissolved during the exposure process. is there.
  • the solubility of the photosensitive adhesive composition in an alkaline aqueous solution becomes difficult to develop, and the coating film in the exposed area 601a remains undissolved and pattern processing cannot be performed sufficiently.
  • the hydroxyl group equivalent in (D) phenol compound can be measured by the method of titrating the solution which mixed (D) phenol compound in the standard alkaline solution.
  • phenol compound examples include, for example, 4-ethylresorcinol, 2-propylresorcinol, 4-butylresorcinol, 4-hexylresorcinol, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4 -Hydroxybenzoic acid, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dihydroxydiphenyl disulfide, 4,4'-dihydroxydiphenyl sulfone, 2,2'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylmethane, 2, 2'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4 '-(1,3-dimethylbutylidene) diphenol, 4,4'-(2-ethylhexylidene) diphenol, 4,4 '-Ethylidenebisphe 2,2′-ethylened
  • the content of the phenolic compound (D) is preferably 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of (A) the alkali-soluble resin (particularly the cyclic olefin resin). Is more preferable.
  • content of a phenol compound is less than the said lower limit, the effect of the sensitivity improvement with respect to the light of the photosensitive adhesive composition and the improvement of the undissolved residue of the coating film 601a may not fully be recognized.
  • the content of the phenol compound exceeds the upper limit, pattern collapse occurs during development and precipitation occurs during freezing storage of the photosensitive adhesive composition.
  • the photosensitive adhesive composition further comprises (D) a phenolic compound (resin) other than a phenolic compound, a leveling agent, an antioxidant, a flame retardant, a plasticizer, if necessary, depending on the purpose of improving characteristics such as sensitivity.
  • a phenolic compound (resin) other than a phenolic compound, a leveling agent, an antioxidant, a flame retardant, a plasticizer, if necessary, depending on the purpose of improving characteristics such as sensitivity.
  • a silane coupling agent, a curing accelerator and the like may be contained.
  • the present invention is not limited to this.
  • arbitrary components may be added to the photosensitive adhesive composition.
  • an arbitrary structure may be added to the semiconductor device.
  • Example 1 Synthesis of Cyclic Olefin Resin A-1 (Polymer) All glass devices were prepared and dried at 60 ° C. and 0.1 Torr (13.3 Pa) for 18 hours. Thereafter, all glass equipment was installed in the glove box.
  • the mixture (reaction solvent) containing each monomer was prepared. Thereafter, purging (nitrogen purging) was performed by flowing nitrogen for 30 minutes while heating the reaction solvent at 45 ° C.
  • EPEsNB (14.2 g, 0.073 mol) and NBTON (46.7 g, 0.159 mol) were mixed with another glass device (glass device Y), and a nitrogen purge was performed.
  • bis (toluene) bis (perfluorophenyl) nickel was put into the glass apparatus Y.
  • the mixture in the glass apparatus X described above was added to the glass apparatus Y over 3 hours at such a rate that the polymerization reaction proceeded at a constant level, to obtain a reaction solution.
  • the solution A is separated into an aqueous layer and an organic layer.
  • the finally obtained polymer was diluted in propylene glycol methyl ether acetate, and the solvent was substituted so that the polymer concentration became 40%. In this way, a polymer (cyclic olefin resin A-1) in a solution state represented by the formula (7) was obtained.
  • the yield of the polymer obtained by the above synthesis was 93.1%, the weight average molecular weight (Mw) of the obtained polymer was 85,900, and the molecular weight dispersion (PD) of the obtained polymer was 2.52.
  • composition of the resulting polymer (cyclic olefin resin A-1), in 1 H-NMR, HFANB 45.0 mol%, 2- (bicyclo [2.2.1] hept-2-ene -
  • EPENB 5-yl propionic acid
  • Photoacid generator B-1 As the photoacid generator B-1, a compound represented by the following formula (8) was prepared.
  • epoxy compound C-1 As the epoxy compound C-1, a compound represented by the following formula (9) was prepared.
  • Antioxidant E-1) A compound represented by the following formula (11) was prepared as the antioxidant E-1.
  • antioxidant E-2 As antioxidant E-2, a compound represented by the following formula (12) was prepared.
  • Cyclic olefin resin A-1 (22.0 parts by weight as solid content), photoacid generator B-1 (5.0 parts by weight), epoxy compound C-1 (5.0 parts by weight), phenol Compound D-1 (3.0 parts by weight), antioxidant E-1 (3.0 parts by weight), antioxidant E-2 (2.0 parts by weight), and propylene glycol methyl ether as a solvent Acetate (60.0 parts by weight including propylene glycol methyl ether acetate contained in the solution of cyclic olefin-based resin A-1) was mixed, and the uniform photosensitive adhesive composition of Example 1 was mixed. Obtained.
  • Examples 2 to 15, Comparative Examples 1 to 6 The raw materials constituting the photosensitive adhesive composition were changed as shown in Tables 1 and 2, and the contents of the respective materials were set as shown in Tables 1 and 2 in the same manner as in Example 1. Thus, a photosensitive adhesive composition was obtained.
  • the raw material used with the photosensitive adhesive composition of each Example and each comparative example is shown below.
  • Polyimide resin A-4 As the polyimide resin A-4, a compound represented by the following formula (19) was prepared. Specifically, 2,2-bis (3-hydroxy-4-aminophenyl) -1, 1,8.13,3-Hexafluoropropane (88.1 g, 0.241 mol), N-methylpyrrolidone (512 g), and toluene (128 g) were charged. The flask was immersed in an oil bath, and 71.9 g (0.229 mol) of 4,4′-oxydiphthalic dianhydride was added to the system over 5 minutes while controlling the temperature of the system at 25 ° C. Then, while introducing dry nitrogen from the gas inlet, the temperature was maintained and the mixture was stirred for 5 hours.
  • the etching process uses a mixed gas of fluorine compound gas (CF 4 ), argon gas (Ar) and oxygen gas (O 2 ), the output is 2500 W, the time is 6 minutes, and the CF 4 flow rate / Ar flow rate / O 2 flow rate is It was performed at 200 sccm / 200 sccm / 50 sccm.
  • the ashing process was performed using a mixed gas of O 2 and Ar, the output was 600 W, the time was 12 minutes, and the O 2 flow rate / Ar flow rate was 50 sccm / 150 sccm.
  • the back grind film used had a width of 25 mm and a length of 75 mm.
  • the back grind film is peeled off from the coating film so that the peel angle is 180 ° from one end in the longitudinal direction of the back grind film, and the average value of the load required for peeling (180 ° peel adhesive strength, unit: N / 25 mm, conforming to JIS Z 0237).
  • the measurement temperature was 25 ° C.
  • the peeling speed was 10.0 ⁇ 0.2 mm / s.
  • adhesive force was not able to be measured.
  • the photosensitive adhesive compositions of Examples and Comparative Examples were applied on a silicon semiconductor chip, pre-baked at 120 ° C. for 5 minutes, and then heat-treated at 150 ° C. for 40 minutes. This obtained the semiconductor chip provided with a coating film.
  • the etching process uses a mixed gas of fluorine compound gas (CF 4 ), argon gas (Ar) and oxygen gas (O 2 ), the output is 2500 W, the time is 6 minutes, and the CF 4 flow rate / Ar flow rate / O 2 flow rate is It was performed at 200 sccm / 200 sccm / 50 sccm.
  • the ashing process was performed using a mixed gas of O 2 and Ar, the output was 600 W, the time was 12 minutes, and the O 2 flow rate / Ar flow rate was 50 sccm / 150 sccm.
  • the back grind film used had a width of 25 mm and a length of 75 mm.
  • the back grind is applied from the paint film so that the peel angle is 180 ° from one end in the longitudinal direction of the back grind film.
  • the film was peeled off, and the average value of the load required for peeling off (180 ° peeling adhesive strength, unit: N / 25 mm, JIS Z 0237 compliant) was determined.
  • the measurement temperature was 50 ° C., and the peeling speed was 10.0 ⁇ 0.2 mm / s.
  • melt viscosity was measured at a frequency of 1 Hz, using a rheometer (Rheo Stress RS150 manufactured by Eihiro Seiki Co., Ltd.) while raising the temperature from 30 ° C. to 200 ° C. at a rate of 10 ° C./min.
  • the minimum value of the measured value from 100 ° C. to 200 ° C. was determined as the minimum melt viscosity of the photosensitive adhesive composition before curing.
  • a temperature cycle test was performed on the obtained 100 semiconductor devices, in which a cycle of holding at a temperature of ⁇ 55 ° C. for 30 minutes and then holding at a temperature of 125 ° C. for 30 minutes was repeated 500 times. After this temperature cycle test, each semiconductor device was observed using an ultrasonic flaw detector. And the observation result was evaluated based on the following evaluation criteria. In addition, in the photosensitive adhesive composition of the comparative example 4, a chip laminated body was not able to be produced.
  • the semiconductor device manufactured using the photosensitive adhesive composition of each example sufficiently suppresses the occurrence of cracks and interfacial peeling even under harsh environments. It was done. As a result, even when the temperature changes suddenly, the adhesive layer adheres and fixes the semiconductor chips well without releasing the adhesion between the semiconductor chips or causing a defect in the semiconductor chips. It shows that. That is, it has been clarified that the photosensitive adhesive composition of the present invention can satisfactorily bond semiconductor chips while relaxing stress concentration in bonding between semiconductor chips.
  • the present invention has industrial applicability.

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Abstract

La présente invention porte sur une composition adhésive photosensible utilisée pour le collage d'un élément à semi-conducteur et d'un élément auquel l'élément à semi-conducteur doit être collé. La composition adhésive photosensible a, après durcissement, un module élastique de 2,0 à 3,5 GPa à une température de 25 °C, la composition adhésive photosensible a, avant durcissement, un module élastique à une température de 25 °C qui est de 70 à 120 % du module élastique à une température de 25 °C de la composition adhésive photosensible après durcissement, la composition adhésive photosensible avant durcissement et après avoir subi un processus de gravure et un processus de calcination a une force d'adhérence à un élément à semi-conducteur de 20 à 200 N à une température de 25 °C et la composition adhésive photosensible a, avant durcissement, une viscosité minimale à l'état fondu de 20 à 500 Pa･s à une température de 100 à 200 °C.
PCT/JP2015/079691 2014-10-22 2015-10-21 Composition adhésive photosensible et dispositif à semi-conducteur WO2016063908A1 (fr)

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KR102242553B1 (ko) * 2019-12-31 2021-04-20 코오롱인더스트리 주식회사 감광성 수지 조성물 및 이를 이용한 드라이 필름 포토레지스트, 감광성 엘리먼트, 회로기판, 및 디스플레이 장치
WO2021076131A1 (fr) * 2019-10-17 2021-04-22 Promerus, Llc Compositions photosensibles et leurs applications
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WO2021076131A1 (fr) * 2019-10-17 2021-04-22 Promerus, Llc Compositions photosensibles et leurs applications
US20210116807A1 (en) * 2019-10-17 2021-04-22 Promerus, Llc Photosensitive compositions and applications thereof
US11537045B2 (en) 2019-10-17 2022-12-27 Promerus, Llc Photosensitive compositions and applications thereof
KR102242553B1 (ko) * 2019-12-31 2021-04-20 코오롱인더스트리 주식회사 감광성 수지 조성물 및 이를 이용한 드라이 필름 포토레지스트, 감광성 엘리먼트, 회로기판, 및 디스플레이 장치

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