JP6477486B2 - Die bond sheet and semiconductor device manufacturing method - Google Patents

Description

  The present invention relates to a die bond sheet and a method for manufacturing a semiconductor device, and more specifically, semiconductor elements such as power semiconductors, LSIs, and light emitting diodes (LEDs), lead frames, ceramic wiring boards, glass epoxy wiring boards, polyimide wiring boards, and the like. The present invention relates to a die bond sheet suitable for bonding to a semiconductor mounting substrate and a method of manufacturing a semiconductor device using the same.

  When manufacturing a semiconductor device, as a method of adhering a semiconductor element and a lead frame (supporting member), a paste-like adhesive in which a filler such as silver powder is dispersed in a resin such as an epoxy resin or a polyimide resin ( For example, there is a method using silver paste). In this method, a paste adhesive is applied to a die pad of a lead frame using a dispenser, a printing machine, a stamping machine, etc., and then a semiconductor element is die-bonded and bonded by heat curing to obtain a semiconductor device.

  In recent years, as the speed and integration of semiconductor elements have increased, high heat dissipation characteristics are also required for adhesives in order to ensure the operational stability of semiconductor devices.

  So far, adhesives aimed at improving thermal conductivity have been proposed. For example, in the following Patent Documents 1 to 5, a die bonding paste (Patent Documents 1 and 2) highly filled with silver particles having high thermal conductivity, a conductive adhesive containing spherical silver powder having a specific particle size ( Patent Document 3), adhesive paste containing solder particles (Patent Document 4), metal powder having a specific particle diameter, and conductive adhesive containing metal ultrafine particles having a specific particle diameter (Patent Document 5) ) Is disclosed.

  In Patent Document 6 below, silver particles are sintered by heating a paste-like silver particle composition comprising non-spherical silver particles subjected to surface treatment and a volatile dispersion medium at 100 ° C. or more and 400 ° C. or less. There has been proposed a technique for forming solid silver having a predetermined thermal conductivity.

JP 2006-73811 A JP 2006-302834 A JP-A-11-66953 JP 2005-93996 A JP 2006-83377 A Japanese Patent No. 4353380

  The paste-like silver particle composition described in Patent Document 6 is considered to be superior in thermal conductivity and connection reliability at high temperatures than other methods because silver particles form metal bonds. However, such a paste-like silver particle composition requires three steps of coating, preliminary drying, and heat sintering. Further, since it contains a solvent, there are problems such as generation of spots due to flow during application, drying, mounting of a semiconductor element and sintering, and generation of voids during drying and sintering.

  On the other hand, when solder is used, die bonding is performed by interposing a sheet-like solder between the substrate and the semiconductor element and heating and melting the solder. In this method, the process can be simplified and the occurrence of spots and voids due to the solvent can be suppressed as compared with the paste. However, soldering has a problem in connection reliability at high temperatures. In addition, there is a problem that even if a metal having a high melting point is simply used instead of solder, bonding becomes difficult.

  The present invention provides a die bond sheet that is excellent in thermal conductivity and connection reliability, and that can join a semiconductor element and a semiconductor element mounting support member in a simple process, and a method for manufacturing a semiconductor device using the same. With the goal.

  The present invention provides a porous sheet having a porosity of 15 to 50% by volume, containing silver and / or copper, and having a carbon content of 1.5% by mass or less, a semiconductor element, and a semiconductor element mounting support member. A semiconductor device manufacturing method is provided in which a semiconductor element and a semiconductor element mounting support member are joined by heating and pressing them.

  According to the method for manufacturing a semiconductor device of the present invention, by using the specific porous sheet, the semiconductor element and the semiconductor element mounting support member can be joined in a simple process, and excellent thermal conductivity is obtained. In addition, a semiconductor device having connection reliability can be obtained.

  The present invention also provides a die bond sheet comprising a porous sheet having a porosity of 15 to 50% by volume, containing silver and / or copper, and having a carbon content of 1.5% by mass or less. To do.

  According to the die-bonding sheet of the present invention, the semiconductor element and the semiconductor element mounting support member can be joined in a simple process, and excellent thermal conductivity and connection reliability can be obtained.

The die bond sheet of the present invention preferably contains 0.06 to 13.6 atomic% of vanadium in terms of atoms and 0.12 to 7.8 atomic% of tellurium in terms of atoms. In this case, adhesion to Ag, Cu, Ni, Al, and SiO ₂ can be improved.

  The porous sheet is preferably obtained by forming a composition containing silver particles and / or copper particles and a dispersion medium into a sheet and heating.

  The present invention can also provide a semiconductor device characterized by having a structure in which a semiconductor element and a semiconductor element mounting support member are bonded via the die bond sheet according to the present invention. The semiconductor device of the present invention can have excellent thermal conductivity and connection reliability when the semiconductor element is bonded to the semiconductor element mounting support member by the die bond sheet according to the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in thermal conductivity and connection reliability, and provides the manufacturing method of the die-bonding sheet | seat which can perform the joining of a semiconductor element and the support member for semiconductor element mounting by a simple process, and a semiconductor device using the same. can do.

It is a schematic cross section showing an example of a semiconductor device according to the present invention. It is a schematic cross section which shows another example of the semiconductor device which concerns on this invention. It is a schematic cross section which shows another example of the semiconductor device which concerns on this invention. It is a schematic cross section which shows another example of the semiconductor device which concerns on this invention. 3 is a SEM image showing a cross section of a die bond sheet before die bonding in Example 1. FIG. 4 is a SEM image showing a cross section of an adhesive layer in a bonded sample using the die bond sheet of Example 1. FIG. 4 is a SEM image showing a cross section of an adhesive layer in a bonded sample using the die bond sheet of Example 1. FIG. It is a SEM image which shows the cross section of the contact bonding layer in the joining sample using the die-bonding sheet | seat of Example 9. FIG. It is a SEM image which shows the interface of the die bond sheet and a copper plate in the joining sample using the die bond sheet of Example 9. It is a SEM image which shows the die bond sheet and interface in the joining sample using the die bond sheet of Example 13. It is a SEM image which shows the die bond sheet and aluminum substrate interface in the joining sample using the die bond sheet of Example 13. It is a SEM image which shows the cross section of the contact bonding layer in the joining sample using the silver foil of the comparative example 1. It is a SEM image which shows the cross section of the contact bonding layer in the joining sample using the die-bonding sheet | seat of Example 19. FIG. It is a SEM image which shows the cross section of the contact bonding layer in the joining sample using the die-bonding sheet of the comparative example 3. It is a SEM image which shows the cross section of the die-bonding sheet | seat of Example 15 before thermocompression bonding. It is a SEM image which shows the cross section of the contact bonding layer (after thermocompression bonding) in the joining sample using the die-bonding sheet | seat of Example 15. FIG.

  Hereinafter, an official embodiment of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted.

  FIG. 1 is a schematic cross-sectional view showing an example of a semiconductor device according to the present invention. A semiconductor device 100 shown in FIG. 1 has a structure in which a semiconductor element 2 and a semiconductor element mounting support member 3 are bonded via a die bond sheet according to the present invention. The die bond sheet 1 to be joined to the semiconductor element 2 and the semiconductor element mounting support member 3 is a die bond sheet according to the invention that has been deformed / modified by heat and pressure, and is after joining. The die bond sheet 1 firmly bonds two adherends by forming a metal bond with the adherend surface 4a of the semiconductor element 2 and with the adherend surface 4b of the semiconductor element mounting support member 3. doing.

  First, the die bond sheet according to the present invention will be described.

  The die bond sheet of the present embodiment is a porous sheet having a porosity of 15 to 50% by volume, containing silver and / or copper, and having a carbon content of 1.5% by mass or less.

  The porous sheet preferably contains gold, silver, and copper as main components from the viewpoints of thermal conductivity, ductility, and connectivity. In particular, silver or copper is preferable from the viewpoint of cost, and an alloy of silver and copper may be used. If metallic components other than silver and copper are contained, it is not preferable because the thermal conductivity is lowered and an oxide film that cannot be easily removed is formed on the surface, which hinders bonding. Therefore, among the elements contained in the porous sheet, the element ratio occupied by silver and / or copper in the element ratio excluding hydrogen, carbon and oxygen is preferably 60 atomic% or more, and 70 atomic% or more. More preferably, it is more preferably 80 atomic% or more.

  The porous sheet is preferably a flat porous sheet made of a continuous silver and / or copper containing pores in the sheet. The porous sheet is preferably composed of a sintered body of silver particles and / or copper particles.

  The die-bonding sheet of this embodiment can contain a glass component as an adhesion aid for the purpose of expanding the types of adherends.

The glass component is preferably sufficiently melted and fluidized at the time of thermocompression bonding of the die bond sheet. From such a viewpoint, a low melting glass having a softening point of 350 ° C. or lower is preferable. Examples of such a low-melting glass include those containing both vanadium, tellurium and silver. For example, 10 to 60% by mass of Ag ₂ O (silver (I) oxide), 5 to 65% by mass of V ₂ O ₅ (divanadium pentoxide), and 15 to 50% by mass of TeO ₂ (tellurium dioxide). And a lead-free glass composition having a total content of Ag ₂ O, V ₂ O ₅ and TeO ₂ of 75% by mass or more is preferable. The low melting point glass further includes P ₂ O ₅ (diphosphorus pentoxide), BaO (barium oxide), K ₂ O (potassium oxide), WO ₃ (tungsten trioxide), MoO ₃ (molybdenum trioxide), Fe _2. One or more of O ₃ (iron oxide (III)), MnO ₂ (manganese dioxide), Sb ₂ O ₃ (antimony trioxide) and ZnO (zinc oxide) may be included.

The die bond sheet of the present embodiment preferably contains 0.06 to 13.6 atomic% of vanadium in terms of atoms and 0.12 to 7.8 atomic% of tellurium in terms of atoms. In this case, adhesion to Ag, Cu, Ni, Al, and SiO ₂ can be improved.

  When the content of vanadium and tellurium is less than the above lower limit value, it means that the low melting point glass is not sufficiently contained, and the effect as an adhesion aid tends to be difficult to obtain. Moreover, when content of vanadium and tellurium exceeds the said upper limit, it means that low melting glass is contained excessively and there exists a tendency for the fall of heat conductivity and the increase in volume resistivity to become remarkable.

  The contents of various elements such as vanadium and tellurium in the die bond sheet can be quantified by fluorescent X-ray measurement, atomic absorption analysis, emission analysis (Atomic Emission Spectrometry), and ICP-MS (Inductively Coupled Plasma-Mass Spectrometry).

  For example, 0.1 g of a die bond sheet is weighed into a plastic container with a lid, 4 mL of nitric acid and 3 mL of hydrogen peroxide are added, and ultrasonic treatment is performed for 30 minutes for dissolution. This is diluted with pure water to obtain a measurement solution. By measuring this measurement solution with an inductively coupled plasma emission spectrometer (SPS5100, manufactured by Hitachi High-Tech Science Co., Ltd.), the contained elements and the ratio thereof can be obtained. Each element emits light at the following wavelengths. V: 292.401 nm, Te: 214.282 nm, W207.912 nm, Ag: 328.068 nm.

When the composition of the material constituting the die bond sheet is known, the porosity can be obtained by the following procedure. First, the die bond sheet is cut into a rectangle, the vertical and horizontal lengths of the die bond sheet are measured with a ruler or an external shape measuring device, and the thickness of the die bond sheet is measured with a film thickness meter to calculate the volume of the die bond sheet. The apparent density M ₁ (g / cm ³ ) is determined from the volume of the cut die bond sheet and the weight of the die bond sheet measured with a precision balance. Using the obtained M ₁ and the density M ₂ (g / cm ³ ) of the material constituting the die bond sheet, the porosity (volume%) is obtained from the following formula (1).
Porosity (volume%) = [1- (M ₁ ) / (M ₂ )] × 100 (1)

In the formula (1), when the material constituting the sheet is a pure 95% by mass or more of silver, when _{M 2} may be a 10.5 g / cm ^3, a purity of 95 mass% or more copper, _{M 2} Can be 8.96 g / cm ³ . If the material constituting the sheet is a mixture of silver and copper, calculated density using additive rule, when the content of copper (wt%) and A, the M ₂ using the following equation (2) can do.
M ₂ (g / cm ³ ) = 1 / [{(A / 100) /8.96} + {(1-A / 100) /10.5}] (2)

When the die bond sheet contains silver and / or copper and low melting point glass, the density M ₂ of the material constituting the die bond sheet is calculated using the following formula (3), and M in the formula (1) _By substituting for ₂ , the porosity is obtained.
M ₂ (g / cm ³ ) = 1 / [{(B / 100) / M ₃ } + {(1−B / 100) / M ₄ }] (3)
[B: Low melting point glass content (% by mass), M ₃ : Low melting point glass density (for example, 5.5 g / cm ³ ), M ₄ : Silver density (for example, 10.5 g / cm ³ ), Copper density (for example, 8.96 g / cm ³ ), density of silver and copper mixture (for example, density M ₂ (g / cm ³ ) calculated by the above formula (2)]

  From the viewpoint of connection reliability, the die bond sheet of this embodiment has a porosity of 15 to 50% by volume, preferably 15 to 40% by volume, and more preferably 15 to 30% by volume. If the porosity is within the above range, the die bond sheet can follow the adherend due to the deformation of the holes when the die bond is crimped, and can exhibit a sufficiently high adhesive force, and the die bond sheet has sufficient mechanical strength. It can be ensured, and it is possible to prevent problems such as breakage and chipping and poor handling.

  The shape of the holes included in the die bond sheet according to the present embodiment may be continuous holes or independent holes. The pores are preferably distributed throughout the die bond sheet.

  The die bond sheet of this embodiment has a carbon content of 1.5% by mass or less, and preferably 1.0% by mass or less. By setting the carbon content to 1.5% by mass or less, it is possible to prevent the formation of a metal bond between the adherend and the die bond sheet by an organic substance or the like, and further, a decomposition gas at a high temperature. This can prevent the connection reliability from deteriorating.

  The carbon content can be measured by an induction heating combustion infrared absorption method.

  The die bond sheet according to the present embodiment can be obtained by forming a composition containing silver particles and / or copper particles and a dispersion medium into a sheet shape and heating.

  Silver particles are particles containing silver atoms, and particles containing 90% by mass or more of silver atoms are preferred. Silver particles may contain silver oxides such as silver oxide, other noble metals such as gold and copper, or oxides thereof in addition to metallic silver. In the present embodiment, when a base metal is included, an oxide film that is difficult to remove is formed on the particle surface and hinders sintering. Therefore, the ratio of the noble metal in the silver particles is preferably 80 atomic% or more, and 90 atomic%. More preferably, it is more preferably 95 atomic% or more.

  Examples of the shape of the silver particles include a spherical shape, a lump shape, a needle shape, and a flake shape. The volume average particle diameter of primary particles of silver particles is preferably 0.01 μm or more and 50 μm or less, more preferably 0.05 μm or more and 30 μm or less, and further preferably 0.1 μm or more and 10 μm or less.

  Silver particles may be treated with a surface treatment agent. However, the surface treating agent is preferably one that can be removed in the process of producing the die bond sheet. Examples of such surface treatment agents include aliphatic carboxylic acids such as palmitic acid, stearic acid, arachidic acid, terephthalic acid and oleic acid, aromatic carboxylic acids such as pyromellitic acid and o-phenoxybenzoic acid, and cetyl alcohol. , Stearyl alcohol, isobornylcyclohexanol, aliphatic alcohols such as tetraethylene glycol, aromatic alcohols such as p-phenylphenol, alkylamines such as octylamine, dodecylamine, stearylamine, fats such as stearonitrile, deconitrile, etc. Silane coupling agents such as group nitriles and alkylalkoxysilanes, and polymer treatment agents such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and silicone oligomers.

  The copper particles are particles containing copper atoms, and particles containing 90% by mass or more of copper atoms are preferable. The copper particles may contain copper oxides such as copper oxide (I) and copper oxide (II), other noble metals such as silver and gold, or oxides thereof in addition to copper metal. Moreover, the core particle | grains which coated the copper particle surface with silver may be sufficient. In the present embodiment, when a base metal is contained, an oxide film that is difficult to remove is generated on the particle surface and hinders sintering. Therefore, the ratio of the noble metal in the copper particles is preferably 80 atomic% or more, and 90 atomic%. More preferably, it is more preferably 95 atomic% or more.

  Examples of the shape of the copper particles include a spherical shape, a lump shape, a needle shape, and a flake shape. The volume average particle size of the primary particles of the copper particles is preferably 0.01 μm or more and 50 μm or less, more preferably 0.05 μm or more and 30 μm or less, and further preferably 0.1 μm or more and 10 μm or less.

  The copper particles may be treated with a surface treatment agent. However, the surface treating agent is preferably one that can be removed in the process of producing the die bond sheet. Examples of such surface treatment agents include aliphatic carboxylic acids such as palmitic acid, stearic acid, arachidic acid, terephthalic acid and oleic acid, aromatic carboxylic acids such as pyromellitic acid and o-phenoxybenzoic acid, and cetyl alcohol. , Stearyl alcohol, isobornylcyclohexanol, aliphatic alcohols such as tetraethylene glycol, aromatic alcohols such as p-phenylphenol, alkylamines such as octylamine, dodecylamine, stearylamine, fats such as stearonitrile, deconitrile, etc. Silane coupling agents such as group nitriles and alkylalkoxysilanes, and polymer treatment agents such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and silicone oligomers.

  The dispersion medium is preferably a volatile one, such as pentanol, hexanol, heptanol, octanol, decanol, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, α-terpineol, bornylcyclohexanol (MTPH) and the like. And polyhydric alcohols, ethylene glycol butyl ether, ethylene glycol phenyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol isobutyl ether, diethylene glycol hexyl ether, triethylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene Glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, propylene glycol propyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, di Ethers such as propylene glycol butyl ether, dipropylene glycol dimethyl ether, tripropylene glycol methyl ether, tripropylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol Ethylene glycol butyl ether acetate, dipropylene glycol methyl ether acetate (DPMA), ethyl lactate, butyl lactate, γ-butyrolactone, esters such as propylene carbonate, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N -Acid amides such as dimethylformamide, aliphatic hydrocarbons such as cyclohexanone, octane, nonane, decane and undecane, aromatic hydrocarbons such as benzene, toluene and xylene, mercaptans having an alkyl group having 1 to 18 carbon atoms, carbon Examples include mercaptans having a cycloalkyl group of 5 to 7. Examples of mercaptans having an alkyl group having 1 to 18 carbon atoms include ethyl mercaptan, n-propyl mercaptan, i-propyl mercaptan, n-butyl mercaptan, i-butyl mercaptan, t-butyl mercaptan, pentyl mercaptan, hexyl mercaptan. And dodecyl mercaptan. Examples of mercaptans having a cycloalkyl group having 5 to 7 carbon atoms include cyclopentyl mercaptan, cyclohexyl mercaptan, and cycloheptyl mercaptan. It is preferable that the compounding quantity of a dispersion medium is 5-50 mass parts with respect to 100 mass parts of silver particles or copper particles.

  When making it adhere | attach with a nonmetal, the said composition may contain a glass component as an adhesion aid. When the glass component is contained, a low melting point glass having a softening point of 350 ° C. or lower is preferable from the viewpoint of sufficiently melting and flowing during thermocompression bonding. In the present embodiment, low melting point glass particles can be blended with the above composition.

The low-melting glass particles, the major component as a 10 to 60 wt% of _Ag 2 O (silver oxide (I)), 5 to 65 wt% of _V 2 _{O 5} and (vanadium pentoxide), 15 to 50 mass % Of TeO ₂ (tellurium dioxide), and a lead-free glass composition having a total content of Ag ₂ O, V ₂ O ₅ and TeO ₂ of 75% by mass or more is preferable. The low-melting glass particles further include P ₂ O ₅ (diphosphorus pentoxide), BaO (barium oxide), K ₂ O (potassium oxide), WO ₃ (tungsten trioxide), MoO ₃ (molybdenum trioxide), Fe _{One or more of 2} O ₃ (iron oxide (III)), MnO ₂ (manganese dioxide), Sb ₂ O ₃ (antimony trioxide) and ZnO (zinc oxide) may be included.

  The volume average particle size of the primary particles of the low-melting glass particles is preferably 0.01 μm or more and 50 μm or less, more preferably 0.05 μm or more and 30 μm or less, and further preferably 0.1 μm or more and 10 μm or less. preferable.

  The blending amount of the low-melting glass particles is preferably 1 part by mass or more and 30 parts by mass or less, preferably 2 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the composition from the viewpoint of adhesiveness of the low melting point glass. It is more preferable that By making the blending amount of the low melting point glass particles within the above range, it becomes easy to obtain the effect of improving the adhesiveness by the low melting point glass, and it is possible to suppress a decrease in thermal conductivity and an increase in volume resistivity, Sufficient characteristics as a die-bonding material can be secured.

  The compounding amount of the low melting point glass particles is such that the vanadium content in the above-described die bond sheet is 0.06 to 13.6 atomic% in terms of atoms, and the tellurium content is 0.12 to 7.8 in terms of atoms. It is preferable to set the atomic%.

  The composition is preferably pasty. The paste-like composition preferably has a Casson viscosity at 25 ° C. of 0.01 Pa · s or more and 10 Pa · s or less, and 0.05 Pa · s or more and 5 Pa · s or less from the viewpoint of application and moldability. More preferred.

  A small amount of an additive may be added to the paste-like composition from the viewpoint of improving the dispersibility and sintering properties of the particles and adjusting the viscosity of the paste.

  The above additives include aliphatic carboxylic acids such as palmitic acid, stearic acid, arachidic acid, terephthalic acid, oleic acid, linoleic acid, phosphorous acid such as diphenyl phosphite, diisopropyl phosphite, dihydroxynaphthoic acid, dihydroxy Aliphatic hydroxycarboxylic acids such as benzoic acid, aromatic hydroxycarboxylic acids such as 3-hydroxy-2-methylbenzoic acid, and the like can be used. Of these, stearic acid is preferred from the viewpoint of improving the dispersibility and sinterability of the particles and adjusting the viscosity of the paste.

  It is preferable that the compounding quantity of an additive is 0.1-5 mass parts with respect to 100 mass parts of metals and glass particles.

  Moreover, even if it is for adjusting the viscosity of a paste-form composition, it is preferable not to contain organic substance, especially binder resin. When such an organic substance or a binder resin is included in the die bond sheet, there is a tendency that the connectivity at the time of die bonding by the die bond sheet and the heat resistance after die bonding are inferior.

  The technique for forming the composition into a sheet may be any technique that allows particles to be deposited in a sheet form on a molded substrate. Examples of such techniques include inkjet printing, super inkjet printing, screen printing, transfer printing, Offset printing, jet printing method, dispenser, jet dispenser, needle dispenser, comma coater, slit coater, die coater, gravure coater, slit coat, letterpress printing, intaglio printing, gravure printing, stencil printing, soft lithograph, bar coat, applicator, particle A deposition method, spray coater, spin coater, dip coater, electrodeposition coating, or the like can be used.

  The molded substrate on which the particles are deposited in the form of a sheet is preferably a plate-like or sheet-like substrate having a flat surface with a 10-point average surface roughness of 20 μm or less from the viewpoint of the smoothness of the molded die-bonded sheet. Moreover, the surface material of a shaping | molding board | substrate does not have adhesiveness with respect to a die-bonding sheet from the necessity of releasing a die-bonding sheet formed through the heating process from a board | substrate. Further, the molded substrate is preferably made of a material having heat resistance that does not deform at a temperature at which silver particles or copper particles are sintered.

  Examples of the material for such a molded substrate include polytetrafluoroethylene, polyimide, and PEEK resin. When the above composition does not contain low-melting glass particles, copper, nickel, aluminum, glass, alumina, silicon nitride, and stainless steel can be used. A substrate having heat resistance and a cloth coated or impregnated with the above material may be used as a molded substrate. However, if the heating process is performed after the composition is formed into a sheet on a molded substrate and then transferred from the molded substrate to another heating process substrate before the heating step, the material of the molded substrate is limited. No, as long as the substrate for the heating process does not have adhesiveness to the die bond sheet.

  The paste-like composition formed into a sheet shape can be appropriately dried from the viewpoint of suppressing flow and void generation during sintering.

  As the drying method, drying at room temperature, drying by heating, or drying under reduced pressure can be used. For heat drying or reduced pressure drying, hot plate, warm air dryer, warm air heating furnace, nitrogen dryer, infrared dryer, infrared heating furnace, far infrared heating furnace, microwave heating device, laser heating device, electromagnetic heating device A heater heating device, a steam heating furnace, a hot plate press device, or the like can be used. The drying temperature and time are preferably adjusted as appropriate in accordance with the type and amount of the used dispersion medium. For example, the drying temperature and time are preferably dried at 50 to 180 ° C. for 1 to 120 minutes.

  Next, it heat-processes with respect to the paste-form composition shape | molded by the sheet form, and sinters. Sintering may be performed by heat treatment or heat and pressure treatment. For heat treatment, hot plate, hot air dryer, hot air heating furnace, nitrogen dryer, infrared dryer, infrared heating furnace, far infrared heating furnace, microwave heating device, laser heating device, electromagnetic heating device, heater heating An apparatus, a steam heating furnace, or the like can be used. Moreover, a hot plate press apparatus, a heated roll press, or the like may be used for the heat and pressure treatment, or the above heat treatment may be performed while applying pressure with a weight.

  The sintering temperature and time may be any temperature and time at which silver and / or copper particles can be sintered. For example, heating at 200 to 300 ° C. for 5 minutes to 2 hours is preferable.

  The copper particles may be sintered in a reducing atmosphere from the viewpoint of removing the surface oxide film. Examples of the reducing atmosphere include a hydrogen atmosphere, a nitrogen atmosphere containing formic acid, and an atomic hydrogen atmosphere.

  The die bond sheet obtained by sintering can be released from the molded substrate and obtained as a self-supporting sheet. The obtained die bond sheet is used for the die bonding step. When the releasability is poor, a blade-like plate can be obtained by being inserted between the obtained die bond sheet and the molded substrate.

  The die bond sheet can be cut to a required size in the die bonding process. Cutting may be performed before releasing from the molded substrate or after.

  The die bond sheet thus produced may be impregnated with a reducing agent for the purpose of removing the oxide film from the metal surface of the adherend. As the reducing agent, phenol compounds such as phloroglucinol and resole, phosphorous acid such as diisopropyl phosphite and diphenyl phosphite, formic acid compounds such as formic acid and ethyl formate, aliphatic compounds such as dihydroxynaphthoic acid and dihydroxybenzoic acid Hydroxycarboxylic acids, aromatic hydroxycarboxylic acid carboxylic acids such as 3-hydroxy-2-methylbenzoic acid, sugars such as glucose and sucrose, polyols such as diglycerin, dipropylene glycol and triethylene glycol, tin chloride (II ) And the like, and oxalic acid and glyoxylic acid.

  The porosity of the die bond sheet can be adjusted by the pressure during the production of the die bond sheet. The pressure condition is preferably 0 to 5 MPa. If the pressure at the time of producing the die bond sheet is within the above range, the porosity included in the sheet is 15% by volume or more, and the sheet is deformed to exhibit a sufficiently high adhesive force to the adherend. it can. On the other hand, when the pressure is higher than the above upper limit, the porosity is less than 15% by volume, and the sheet is difficult to deform during pressure bonding, and there is a tendency that a gap is formed between the joining surface and the sheet. Such voids are not preferable because they increase the local thermal resistance, lower the adhesive force, and become the starting point of breakage due to thermal stress, and lower the connection reliability.

  The carbon content in the die bond sheet can be adjusted by appropriately selecting the components to be blended in the paste-like composition and the sintering conditions. Specifically, it is preferable not to include a binder resin in the paste-like composition. Further, the dispersion medium to be blended in the paste-like composition is preferably volatile. Examples of the method for adjusting the viscosity of the paste-like composition to the above preferable range using a volatile dispersion medium include, for example, adjustment of particle concentration, adjustment of particle shape, particularly aspect ratio and particle size, isobornylcyclohexanol, and the like. The use of a high-viscosity dispersion medium such as

  Moreover, it is preferable that the surface treatment agent of silver particles and / or copper particles is volatile or thermally decomposable from the viewpoint of lowering the carbon content in the die bond sheet.

  For example, by performing sintering at 200 to 300 ° C. for 30 minutes to 2 hours using the paste-like composition, the carbon content contained in the die bond sheet can be adjusted to 1.5 mass% or less.

  The thickness of the die bond sheet can be appropriately set according to the surface roughness of the semiconductor element as the adherend and the semiconductor element mounting support member and the connection reliability after bonding. In the die bond sheet of the present invention, the hole in the die bond sheet is crushed by thermocompression bonding so that the die bond sheet and the adherend surface are in close contact with each other to form a metal bond. Therefore, the thickness of the die bond sheet needs to be a thickness that allows the die bond sheet to compress and deform and absorb the surface irregularities of the semiconductor element and the semiconductor element mounting support member, and is preferably 10 μm or more, preferably 20 μm or more. It is more preferable that Moreover, since it is not preferable that the semiconductor element is embedded in the die bond sheet, it is preferable that the die bond sheet is thinner than the thickness of the semiconductor element. Generally, this thickness is 600 μm or less.

  The semiconductor device 100 shown in FIG. 1 is obtained by interposing the above-described die bond sheet between the semiconductor element 2 and the semiconductor element mounting support member 3 and heating and pressing them.

  Heating and pressing can be performed by a thermocompression bonding apparatus. As a thermocompression bonding apparatus, a hot plate press apparatus, a heating roll press, or the like may be used, or heat treatment may be performed while applying pressure with a weight.

  The temperature during thermocompression bonding is preferably 220 ° C. or higher, and more preferably 250 ° C. or higher, from the viewpoint of obtaining sufficient adhesive strength. The upper limit of the thermocompression bonding temperature is set by the heat-resistant temperature of the device, can be 400 ° C. or lower, and can be 350 ° C. or lower.

The pressure during thermocompression bonding is preferably 1 MPa or more, more preferably 5 MPa or more, further preferably 7 MPa or more, and particularly preferably 10 MPa or more, from the viewpoint of adhesion. If the pressure is not applied, the adhesion between the die bond sheet and the adherend due to the deformation of the sheet is difficult to obtain, and there is a tendency that sufficient adhesive force cannot be obtained. On the other hand, the upper limit value of the thermocompression bonding pressure is preferably 35 MPa or less, and more preferably 20 MPa or less, from the viewpoint of preventing the semiconductor element and the semiconductor element mounting support member from being damaged.
The die shear strength of the joined body after thermocompression bonding is preferably 20 MPa or more. In particular, the die shear strength with respect to the semiconductor element and the substrate provided with silver plating is preferably 20 MPa or more.

  The atmosphere during thermocompression bonding is preferably carried out in air or in an inert gas if the adherend is a combination of a non-oxidizing material to be adhered and a die bond sheet containing silver. . As the inert gas, nitrogen containing no oxygen or a rare gas is preferable.

  On the other hand, if an adherend having an oxide film on the adherend surface and having a metal that is relatively easily reduced and a die bond sheet containing copper, thermocompression bonding is performed while removing the oxide film in a reducing atmosphere. Can be implemented. Examples of such a reducing atmosphere include a hydrogen atmosphere or a nitrogen atmosphere containing formic acid. At this time, hydrogen gas may be activated by using a hot wire method, an RF plasma method, or a surface wave plasma method. Alternatively, a reducing agent may be impregnated in the die bond sheet instead of the reducing atmosphere, and thermocompression bonding may be performed in an inert gas.

  In order to reduce damage to the semiconductor element and the semiconductor element mounting support member during thermocompression bonding, or to increase the uniformity of pressure and temperature, between the stacked semiconductor element or the semiconductor element mounting support member and the hot plate A protective sheet may be provided. The protective sheet may be made of a material that can withstand the temperature during thermocompression bonding and is softer than the adherend to be contacted. Examples of such a material include polyimide, fluororesin, aluminum, copper, and carbon.

  When the material is silver, the porosity of the die bond sheet after thermocompression bonding is preferably 10% by volume or less, more preferably 8% by volume or less, and further preferably 5% by volume or less. preferable. On the other hand, when the material is copper, it is preferably 15% by volume or less, more preferably 10% by volume or less, and still more preferably 6% by volume or less. Since copper has a higher elastic modulus than silver, the same or higher strength can be obtained even with a porosity higher than that of a silver die bond sheet. A die bond sheet is interposed between a semiconductor element and a semiconductor element mounting support member, and heat bonding is performed so as to achieve such a porosity, so that the voids are deformed when the die bond sheet is pressed and bonded. In addition to exhibiting a sufficiently high adhesive force, the mechanical strength of the die bond sheet can be sufficiently secured, and the reliability against thermal shock and thermal stress due to power cycle can be secured.

  The porosity of the die bond sheet after the thermocompression bonding can be measured by a method of calculating from the area ratio of the hole portion and the dense portion from the SEM image of the cross section. For example, it can be measured by the following method. The pressure-bonded sample is poured with epoxy casting resin so that the entire sample is filled and cured. The cast sample is cut near the cross section to be observed, the cross section is cut by polishing, and the cross section is processed by a CP (cross section polisher) processing machine. A cross-sectional image is obtained by observing a cross section with an SEM apparatus (for example, TM-1000, manufactured by Hitachi High-Technologies Corporation). The ratio of the holes included in the cross-section is the ratio of the number of dots to the cross-section by measuring the number of dots by selecting the hole using the image processing software and calculating the weight ratio by printing an image Or a method of calculating the porosity from the area ratio of the hole portion occupying the cross section by adjusting the threshold value for the image of the cross section, binarizing the hole portion and the dense portion into white / black Etc. can be obtained. As image processing software, Adobe Photoshop series (manufactured by Adobe Systems Co., Ltd.), paint tool SAI series (SYSTEMX Corporation), GIMP (manufactured by the GIMP development team.), Core PrintShop Pro series (manufactured by Corel Corporation), Image Corporation US National Institutes of Health), but is not limited to these.

Furthermore, as the conditions at the time of thermocompression bonding, when the porosity of the die bond sheet before thermocompression bonding is V ₁ % by volume and the porosity of the die bond sheet after thermocompression bonding is V ₂ % by volume, V ₂ / V ₁ Is preferably 0.37 or less, more preferably 0.31 or less, and even more preferably 0.19 or less. By thermocompression bonding under such conditions, the die bond sheet can follow the adherend due to deformation of the pores during crimping, and can exhibit sufficiently high adhesive force, and the die bond sheet has sufficient mechanical strength. It is possible to ensure the reliability against thermal stress caused by thermal shock or power cycle.

  The thickness of the die bond sheet after thermocompression bonding is preferably 80% or less, more preferably 76% or less, and further preferably 64% or less as compared with that before thermocompression bonding. By bonding so that the thickness of the die-bonding sheet after thermocompression bonding is in the above range, the die-bonding sheet can follow the adherend due to deformation of the pores during press-bonding, and can exhibit sufficiently high adhesive force. At the same time, the mechanical strength of the die bond sheet can be sufficiently secured, and the reliability against thermal shock and thermal stress due to power cycle can be secured.

  The porosity and / or thickness after thermocompression bonding can be adjusted by the pressure during thermocompression bonding. Such a pressure can be appropriately set by those skilled in the art within the above-described pressure range during thermocompression bonding.

  The die bond sheet of this embodiment can also be used for manufacturing a semiconductor device having a structure different from that of the semiconductor device shown in FIG. For example, FIG. 2 is a schematic cross-sectional view showing another example of the semiconductor device according to the present invention. The semiconductor device 102 shown in FIG. 2 includes a semiconductor element mounting support member 3 and a plurality of semiconductor elements 2a and 2b. Has a structure bonded via a die bond sheet 1. 3 is a schematic cross-sectional view showing another example of the semiconductor device according to the present invention. The semiconductor device 104 shown in FIG. 3 includes a semiconductor element 2 and a semiconductor element mounting support member 3 having a plurality of die bonds. It has a structure joined via sheets 1a and 1b. In the semiconductor device 104, the thickness of the die bond layer can be increased and the followability to a non-smooth deposition surface can be improved.

  FIG. 4 is a schematic cross-sectional view showing an example of a semiconductor device manufactured using the die bond sheet of this embodiment. A semiconductor device 106 shown in FIG. 4 includes a semiconductor element 2 connected via a die bond sheet 1 according to the present embodiment on a lead frame 5a, and a mold resin 7 for molding them. The semiconductor element 2 is connected to the lead frame 5 b through the wire 6.

  A semiconductor device obtained by using the die bond sheet according to the present embodiment includes a power module including a diode, a rectifier, a thyristor, a MOS gate driver, a power switch, a power MOSFET, an IGBT, a Schottky diode, a fast recovery diode, a transmitter, Examples include amplifiers and LED modules. The power module, transmitter, amplifier, and LED module obtained using the die bond sheet according to the present embodiment can have high adhesion between the semiconductor element and the semiconductor element mounting support member.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

<Preparation of paste-like composition>
Pasty compositions 1-10 were prepared according to Preparation Examples 1-10 below. In addition, in Tables 1-3, the compounding quantity of each component is shown by a mass part.

The symbol of each component in Tables 1-3 means the following.
AgC239: Silver particles (Fukuda Metal Foil Powder Co., Ltd., product name “AgC239”, volume average particle size 3.0 μm).
K-0082P: Silver particles (manufactured by METALOR, product name “K-0082P”, volume average particle size 1.6 μm).
Silver foil: Silver foil (manufactured by Alfa Aesar, product name “Silver Foil 0.1 mm thick hard Prem. 99.998%, thickness 100 μm)
Cu-HWQ: copper particles (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., product name “Cu-HWQ”, volume average particle size 1.5 μm).
Nanotech CUO: Copper oxide particles (manufactured by CIK Nanotech, product name “Nanotech CUO”, volume average particle size 70 μm).
CH-002: Spherical copper particles (manufactured by Mitsui Kinzoku Co., Ltd., product name “CH-002”, volume average particle size 0.3 μm)
Cupric oxide: (Wako Pure Chemical Industries, product name “Copper (II) oxide”).
3L3: (Fukuda Metal Foil Powder Co., Ltd., product name “3L3”, volume average particle size 10 μm flake shape)
Stearic acid: (New Nippon Rika Co., Ltd., product name "Stearic acid").
VP-1300: Low melting point glass particles (manufactured by Hitachi Chemical Co., Ltd., product name “Bunnytect III VP-1300”, volume average particle size 1 μm).
MTPH: (manufactured by Nippon Terpene Kogyo Co., Ltd., product name “Bornylcyclohexanol”).
DPMA: (manufactured by Daicel Chemical Industries, product name “dipropylene glycol methyl ether acetate”).
Polypropylene carbonate: (product name “4-methyl-1,3-dioxolan-2-one, manufactured by Wako Pure Chemical Industries, Ltd.).
Terpineol: (Wako Pure Chemical Industries, product name “α-terpineol”).
Polyamic acid: (manufactured by Aldrich, product name “Poly (pyromeric dianhydride-co-oxydiline) NMP solution”).

(Preparation Example 1)
Boronyl cyclohexanol (MTPH, manufactured by Nippon Terpene) as a dispersion medium and 6.83 g of dipropylene glycol methyl ether acetate (DPMA, manufactured by Daicel Chemical) and stearic acid (manufactured by Nippon Nippon Chemical Co., Ltd.) as additives. 1.35 g was mixed into a plastic bottle, sealed, warmed in a 50 ° C. water bath, and made into a clear and uniform solution with occasional shaking. To this solution, 135 g of AgC239 as silver particles was added and stirred with a spatula until there was no dry powder. Further, the mixture was sealed and stirred for 1 minute at 2000 rpm using a rotation and revolution type stirring device (Planetary Vacuum Mixer ARV-310, manufactured by Sinky Corporation) to obtain a paste-like composition 1.

(Preparation Example 2)
Add 3.2 g of propylene carbonate as a dispersion medium, 14.28 g of Cu-HWQ (made by Fukuda Metal Foil Powder Co., Ltd.) as copper particles, and 2.52 g of Nanotech CUO (made by CIK Nanotech) as copper oxide particles to a poly bottle. Stir with a spatula until the dry powder is gone. Thereafter, a paste-like composition 2 was obtained in the same manner as in Preparation Example 1.

(Preparation Examples 3 to 7)
Mix 1.37 g of terpineol (manufactured by Wako Pure Chemical Industries) as a dispersion medium and 0.14 g of stearic acid (manufactured by Shin Nippon Rika Co., Ltd.) as an additive in a plastic bottle, seal and warm in a 50 ° C. water bath, and occasionally shake A clear and uniform solution was obtained. Table 2 shows Bunnytect III VP-1300 (manufactured by Hitachi Chemical Co., Ltd.) and two types of silver particles (AgC239 (manufactured by Fukuda Metal Foil Industry Co., Ltd.), K-0082P (manufactured by METALOR)) which are low melting glass particles. The mixture was added at the indicated ratio and stirred with a spatula until there was no dry powder. Thereafter, paste-like compositions 3 to 7 were obtained in the same manner as in Preparation Example 1.

(Preparation Example 8)
10 g of terpineol as a dispersion medium and 90 g of spherical copper particles (CH-002, manufactured by Mitsui Kinzoku Co., Ltd.) as copper particles are mixed in a plastic bottle, and stirred for 2 minutes at 2000 rpm using an automatic revolution type stirring device. A composition 8 was obtained.

(Preparation Example 9)
Two zirconia pots with 10 zirconia balls (10 mm in diameter) and 10 g of cupric oxide (manufactured by Wako Pure Chemical Industries, Ltd.) are put together, and zirconia pots are attached to both sides of the planetary ball mill (P7, manufactured by Fritsch) at 450 rpm. Milled for 2 hours. 18 g of pulverized cupric oxide and 2 g of dipropylene glycol monobutyl ether were mixed in a plastic bottle and stirred with a spatula. This mixture was stirred at 2000 rpm for 1 minute using an automatic revolution type stirring device to obtain a paste-like composition 9.

(Preparation Example 10)
As a dispersion medium, 4 g of terpineol and 18 g of flaky copper powder (3L3, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) are mixed in a plastic bottle and stirred at a reduced pressure of 2 kPa and 2000 rpm for 2 minutes using an automatic revolving stirrer. A paste-like composition 10 was obtained.

<Production of die bond sheet>
Example 1
Paste composition 1 was applied in a film form on a glass plate using a Baker applicator (YBA5 type, manufactured by Yoshimitsu Seiki Co., Ltd.) with a gap set at 100 μm. The glass plate was heated from room temperature to 200 ° C. at 10 ° C./min on a hot plate, and then allowed to stand at 200 ° C. for 1 hour. After returning this glass substrate to room temperature (25 degreeC), the cured film of the paste-form composition 1 was obtained as a self-supporting film | membrane by inserting and peeling the blade of a cutter knife between glass and a cured film. This cured film was cut into a square of 14 × 14 mm ² to obtain a die bond sheet. Using a digital linear gauge (DG-525H, manufactured by Ono Sokki Co., Ltd.), the difference between the glass substrate thickness and the total thickness of the glass substrate and the die bond sheet was measured as the film thickness of the die bond sheet. It was.

  About the obtained die-bonding sheet, various measurements and analyzes were performed according to the following methods. The results are summarized in Tables 1 and 2.

[Carbon content measurement]
In order to evaluate the amount of organic matter contained in the die bond sheet, the carbon content was measured by an induction heating combustion infrared absorption method. When the carbon content is below the detection limit (10 ppm), it is indicated by “−” in the table.

[Analysis of contained elements]
The element ratio contained in the die bond sheet was quantified by the following emission analysis. First, about 0.1 g of a die bond sheet was weighed to 4 digits after the decimal point in a plastic container with a lid. To this, 4 mL of nitric acid (AA-100, manufactured by Tama Chemical Co., Ltd.) and 3 mL of hydrogen peroxide (for atomic absorption measurement, manufactured by Wako Pure Chemical Industries, Ltd.) were added and subjected to ultrasonic treatment for 30 minutes to dissolve the die bond sheet. After confirming that there was no residue or suspended solids, it was transferred to a 100 mL volumetric flask, and pure water was added while washing the plastic container with the lid, and diluted to 100 mL. It was further diluted as necessary to obtain a measurement solution. The contained element and its ratio were obtained by measuring the measurement solution with an inductively coupled plasma emission spectrometer (SPS5100, manufactured by Hitachi High-Tech Science Co., Ltd.). The measurement was performed under the following conditions. Plasma output: 1.2 kW, measurement wavelength: V: 292.401 nm, Te: 214.282 nm, W: 207.9912 nm, Ag: 328.068 nm.

[Die shear strength measurement]
A die-bonded sheet of 14 × 14 mm ^{2 is} placed on a silver-plated alumina DCB substrate, on which titanium, nickel and gold are plated in this order, and a silicon chip having a 2 × 2 mm ² deposition surface is gold-plated 16 The sheets were placed side by side, and the expanded graphite sheet was placed on top of each other, and a heat pressure bonding apparatus (manufactured by Tester Sangyo Co., Ltd.) was used for bonding for 10 minutes at 10 MPa and 300 ° C. in air. The bond strength of the die bond sheet was evaluated by die shear strength. Using a universal bond tester (4000 series, manufactured by DAGE) equipped with a DS-100 load cell, press a silicon chip with a measurement speed of 5 mm / min, a measurement height of 50 μm and a gold-plated surface in the horizontal direction, and die bond sheet The die shear strength was measured. The average value of the values obtained by measuring 15 silicon chips was defined as the die shear strength.

For the measurement of die shear strength, Ag, Cu, Ni, Al or SiO ₂ is prepared as a substrate material. When the substrate material is Ag, it is under an air atmosphere or a nitrogen atmosphere, and when it is SiO ₂ or Al, it is under a nitrogen atmosphere, Cu, In the case of Ni, thermocompression bonding was performed using an atmosphere-controlled thermocompression bonding apparatus (RF-100B, manufactured by Ayumi Kogyo Co., Ltd.) in accordance with the method described in [Measurement of die shear strength] in a formic acid-containing nitrogen atmosphere, and die shear strength was measured. . As a result, the die bond sheet of Example 1 exhibited a die shear strength of 50 MPa or more, which is a measurement limit, with respect to Ag, Cu, and Ni, and had sufficient adhesive strength.

(Examples 2 to 8)
The die shear strength was measured according to the method described in [Measurement of die shear strength] except that the die bonding sheet of Example 1 was changed to the conditions shown in Table 1 for the crimping conditions by the thermocompression bonding apparatus. As a result, it was confirmed that when the temperature was 250 ° C. or higher, the pressure was 1 MPa or higher, and the time was 90 seconds or longer, the die shear strength was 10 MPa or higher and sufficient adhesive strength was obtained.

Example 9
Paste composition 2 was applied in a film form on a glass plate using a Baker applicator (YBA5 type, manufactured by Yoshimitsu Seiki Co., Ltd.) with a gap set at 100 μm. This glass plate was heated at 300 ° C. for 1 hour in a formic acid reflow apparatus “SR-300-2” (manufactured by Ayumi Kogyo Co., Ltd.) in nitrogen containing formic acid (the formic acid content was 10% by mass at 30 ° C. saturation) After sintering, the substrate was allowed to stand in nitrogen at 300 ° C. for 10 minutes, then cooled to 50 ° C. or lower in nitrogen and then taken out into the air. The cured film of the paste-like composition 2 was obtained as a self-supporting film by inserting a blade of a cutter knife between the glass and the cured film and peeling off. This cured film was cut into a square of 14 × 14 mm ² to obtain a die bond sheet. Using a digital linear gauge (DG-525H, manufactured by Ono Sokki Co., Ltd.), the difference between the glass substrate thickness and the total thickness of the glass substrate and the die bond sheet was measured as the film thickness of the die bond sheet. It was. Various measurements and analyzes were performed in the same manner as in Example 1 using this die bond sheet.

  The die shear strength test piece of this die bond sheet is formic acid-containing using an atmosphere control thermocompression bonding apparatus (RF-100B, manufactured by Ayumi Kogyo Co., Ltd.) using a silver-plated alumina DCB (Direct Copper Bond) substrate and a copper plate as a substrate. The die shear strength was measured according to the method described in [Measurement of Die Shear Strength] except that crimping was performed in a nitrogen atmosphere. As a result, the die shear strength of the die bond sheet of Example 9 was 20 MPa for the silver-plated alumina DCB substrate and 22 MPa for the copper plate, and both showed sufficient adhesive strength.

(Examples 10 to 14)
A die bond sheet was produced in the same manner as in Example 1 except that the paste-like compositions 3 to 7 were applied onto a PTFE (tetrafluoroethylene) impregnated glass cloth fixed on a glass substrate with a polyimide tape. Various measurements and analyzes were performed in the same manner as in Example 1 using this die bond sheet.

Using a die bonding sheet prepared from a paste-like composition 3 to 7, Ag, Cu, Ni, Al or SiO2 was prepared as a substrate material, the substrate material is Ag, under a nitrogen atmosphere when the _SiO 2, Al, Cu, Ni In this case, thermocompression bonding was performed using an atmosphere-controlled thermocompression bonding apparatus (RF-100B, manufactured by Ayumi Kogyo Co., Ltd.) in a formic acid-containing nitrogen atmosphere according to the method described in [Measurement of die shear strength] to measure die shear strength. The results are shown in Table 2. In the die bond sheet of Example 12 to which the low melting point glass particles were added, adhesion to Ag, Cu, Ni, Al, and SiO ₂ was obtained.

(Example 15)
A Teflon (registered trademark) -impregnated glass cloth sheet was fixed on an aluminum plate with a polyimide tape, and a paste-like composition 8 was applied in a film shape using a Baker applicator having a gap of 150 μm. This aluminum plate was introduced into a formic acid reflow apparatus and allowed to stand for 10 minutes under reduced pressure. Thereafter, the aluminum plate was heated at a pressure of 0.09 MPa in a formic acid-containing nitrogen atmosphere, and was treated for 1 hour in a state of reaching 385 ° C. Thereafter, this was decompressed at 385 ° C. and allowed to stand for 10 minutes, then returned to normal pressure with nitrogen, transferred to the cooling plate in the front chamber together with the carrier tray, cooled to 30 ° C., and taken out into the air. The cured film of the paste-like composition 8 was obtained as a self-supporting film by inserting a blade of a cutter knife between the glass and the cured film and peeling off. This self-supporting film was cut into a square of 14 × 14 mm ² to obtain a die bond sheet.

A die bond sheet prepared from the paste-like composition 8 is placed on a copper plate (19 × 25 mm, thickness 3 mm), and four copper chips (2 × 2 mm ² ) are arranged in four rows on it, and an alumina plate is placed thereon. (14 × 14 mm ² , thickness 1 mm) and an expanded graphite sheet (14 × 14 mm ² , thickness 0.5 mm) were stacked in this order. This was treated with an atmosphere-controlled thermocompression bonding apparatus (RF-100B, manufactured by Ayumi Kogyo Co., Ltd.) in a formic acid-containing nitrogen atmosphere at 30 MPa and 385 ° C. for 60 minutes, and thereafter treated in nitrogen at no pressure 300 ° C. for 10 minutes. did.

  Except for using this joined body, the die shear strength was measured according to the method described in [Measurement of die shear strength]. As a result, the die bond sheet of Example 15 was judged to have a die shear strength of 50 MPa or more because the copper chip was broken rather than the die bond layer at around 50 MPa.

(Example 16)
An opening of 20 × 20 mm ² was provided on a Teflon (registered trademark) sheet having a thickness of 300 μm to form a mask. This mask was overlaid on a quartz glass plate, paste-like composition 9 was applied to the mask opening, leveled with a metal squeegee, and the mask was removed. The glass plate was dried on a hot plate at 110 ° C. for 10 minutes and then set on a tube heater (made by ALL VACUUM CREATE). Thereafter, the glass plate was treated at 350 ° C. for 1 hour in a hydrogen atmosphere, and then nitrogen was passed and the mixture was allowed to cool and taken out into the air near room temperature. The cured film of the paste-like composition 9 was obtained as a self-supporting film by inserting a blade of a cutter knife between the glass and the cured film and peeling off. This self-supporting film was cut into a square of 14 × 14 mm ² to obtain a die bond sheet.

  The die shear strength was measured by the same method as in Example 15 except that a die bond sheet produced from the paste-like composition 9 was used. As a result, the die bond sheet produced from the paste-like composition 9 had a die shear strength of 50 MPa or more.

(Example 17)
A Teflon (registered trademark) sheet having a thickness of 300 μm is provided with a 20 × 20 mm ² opening as a mask, this mask is overlaid on a quartz glass plate (27 × 35 mm ² ), a paste-like composition 10 is applied, and a metal squeegee is applied. And the mask was removed. This quartz glass plate was introduced into a formic acid reflow apparatus, decompressed and left for 10 minutes. Thereafter, the quartz glass plate was heated at a pressure of 0.09 MPa in a formic acid-containing nitrogen atmosphere and treated for 1 hour in a state of reaching 385 ° C. Thereafter, this was decompressed at 385 ° C. and allowed to stand for 10 minutes, then returned to normal pressure with nitrogen, transferred to the cooling plate in the front chamber together with the carrier tray, cooled to 30 ° C., and taken out into the air. The cured film of the paste-like composition 10 was obtained as a self-supporting film by inserting a blade of a cutter knife between the glass and the cured film and peeling off. This self-supporting film was cut into a square of 14 × 14 mm ² to obtain a die bond sheet.

  The die shear strength was measured in the same manner as in Example 15 except that a die bond sheet produced from the paste-like composition 10 was used. As a result, the die bond sheet produced from the paste-like composition 10 has a die shear strength of 50 MPa or more.

(Comparative Example 1)
A silver foil having a thickness of 100 μm (Silver Foil, 0.1 mm thick, hard, 99.998%, PREMION, manufactured by Alfa Aesar) was cut into a square of 14 × 14 mm 2 and used as a die bond sheet. Various measurements and analyzes were performed in the same manner as in Example 1 using this die bond sheet. As a result, the die shear strength of the die bond sheet of Comparative Example 1 was as low as 8 MPa, indicating poor adhesion.

(Comparative Example 2)
The die bond sheet of Example 1 was impregnated with a polyamic acid (product number 575801, manufactured by Aldrich) solution diluted to 5% by mass with N-methylpyrrolidone so as not to overflow from the surface. Thereafter, an excess polyamic acid solution was wiped off with Bencot (registered trademark, Asahi Kasei Fibers Corporation), and then dried on a hot plate heated to 100 ° C. with a polytetrafluoroethylene sheet. The die bond sheet in which the weight increase in the dry state of the die bond sheet was 1.03% by mass (polyamic acid content 2.8% by mass) was prepared by repeating the impregnation and drying of the polyamic acid solution. Various measurements and analyzes were performed in the same manner as in Example 1 using this die bond sheet. As a result, the die shear strength of the die bond sheet of Comparative Example 2 was as low as 2 MPa, indicating poor adhesion.

<Observation of cross-sectional morphology>
A sample in which a silicon chip and a substrate are bonded with a die bond sheet is fixed in a cup with a sample clip (Sampklip I, manufactured by Buehler), and an epoxy casting resin (Epomount, manufactured by Refinetech) is embedded around the entire sample. Poured, left in a vacuum desiccator, degassed by reducing the pressure for 1 minute. Then, after leaving at room temperature (25 ° C.) for 10 hours, the epoxy casting resin was cured for 2 hours with a 60 ° C. thermostat. Using a refine saw low (Refinetech) equipped with a diamond cutting wheel (11-304, Refinetech), the cast sample was cut in the vicinity of the cross section to be observed. The cross section was shaved with a polishing apparatus (Refine Polisher HV, manufactured by Refinetech) equipped with water-resistant abrasive paper (Carbo Mac paper, manufactured by Refinetech) to give a silicon chip with no cracks. Thereafter, the cross section was smoothed with a polishing apparatus in which a buffing cloth dyed with a buffing abrasive was set. The cross section was measured with an ion milling device (IM4000, manufactured by Hitachi, Ltd.) under conditions of an ion beam irradiation angle of 30 °, an eccentricity of 2 mm, an acceleration voltage of 6 kV, an argon gas flow rate of 0.07 to 0.1 cm ³ / min, and a processing time of 5 minutes. Flat milling was performed, and platinum was sputtered to a thickness of 10 nm using a sputtering apparatus (ION SPUTTER, manufactured by Hitachi High-Tech) on the cross section to obtain a sample for SEM. The SEM sample (ESEM XL30, manufactured by Philips) was used to observe the cross section of the die bond sheet at an applied voltage of 10 kV and various magnifications.

  The processed cross section of the die bond sheet of Example 1 was observed according to the above method, and the cross sectional morphology before joining was observed. FIG. 5 is an SEM image obtained as a result of observing the cross-sectional morphology of the die bond sheet 8a before bonding in Example 1 at 1000 times.

A 14 × 14 mm ² die bond sheet is placed on the silver-plated alumina DCB substrate 10, and titanium, nickel and gold are plated in this order, and a 12.5 × 12.5 mm ² deposition surface is gold plated. In addition, an atmosphere control thermocompression bonding apparatus (RF-100B, manufactured by Ayumi Kogyo Co., Ltd.) with an expanded graphite sheet having a size of 13 × 13 mm ² disposed thereon is further used. A bonded sample 1 was obtained after treatment for 10 minutes.

  The processed cross section of the bonded sample 1 was observed according to the method described in <Observation of sectional morphology>. As a result of observing the cross-sectional morphology of the adhesive layer in the die bond sheet 8b of Example 1 at 1000 times, the SEM image of FIG. 6 was obtained, and as a result of observing at 5000 times, the SEM image of FIG. 7 was obtained. In FIG. 6, 8b is a die bond sheet, and 9 is a silicon chip.

  As shown in FIGS. 6 and 7, the die bond sheet 8 b of Example 1 was compressed to a thickness of 55 μm to 44 μm while the internal pores were crushed by thermocompression bonding. With this deformation, the die bond sheet of Example 1 was compressed. 8b followed the silver plating layer 11 on the substrate which is the adherend surface without any gap. Furthermore, as FIG.6 and FIG.7 shows, the die-bonding sheet | seat 8b of Example 1 formed the metal bond and joined with the silver plating layer 11 which is an adhesion surface.

  Then, using a copper plate as a substrate and using the die bond sheet of Example 2 as a die bond sheet, press bonding was performed in a formic acid-containing nitrogen atmosphere by an atmosphere controlled thermocompression bonding apparatus (RF-100B, manufactured by Ayumi Kogyo Co., Ltd.). The joined sample 2 was obtained in the same manner as the method described in <1.

  According to the method described in <Observation of cross-sectional morphology>, the cross-sectional morphology of the processed sample was observed for the bonded sample 2. As a result of observing the cross-sectional morphology of the adhesive layer by the die bond sheet of Example 2 at 200 times, the SEM image of FIG. 8 was obtained, and as a result of observing at 20000 times, the SEM image of FIG. 9 was obtained.

  As shown in FIG. 8, like the die bond sheet 8b of Example 1, the die bond sheet 12 of Example 2 was compressed to a thickness of 150 μm to 54 μm while the internal pores were crushed by thermocompression, and this change Accordingly, the die bond sheet 12 of Example 2 followed the copper plate 13 as the adherend surface without any gap. Furthermore, as FIG. 9 shows, the die-bonding sheet 12 of Example 2 was joined to the copper plate 13 as the adherend surface without any boundary, and was joined by metal bonding.

  10 and 11 show that the die bond sheet 14 of Example 13 is used when the adherend is a surface silicon oxide substrate (deposition surface: SiO 2) 15 and an aluminum substrate (deposition surface: Al) 16. FIG. 3 is an SEM image obtained as a result of observing a cross section of the bonded samples 3 and 4 prepared in the same manner as in Example 1 and observing the bonded samples according to the method described in <Observation of Cross-sectional Morphology>. 10 and FIG. 11, compared with FIG. 6 and FIG. 7 which are SEM images of the bonded sample of the die bond sheet 8b of Example 1, the die bond sheet 14 of Example 13 containing a glass component has more voids. It was decreased and the density was improved. This is presumably because the low melting point glass melted and flowed during pressure bonding to fill the holes.

  Furthermore, the joining sample 5 was obtained by the method similar to observation of the die-bonding sheet of Example 1 except having used the die-bonding sheet which consists of silver foil of the comparative example 1 for a die-bonding sheet.

  According to the method described in <Observation of cross-sectional morphology> of the bonded sample 5, the cross-sectional morphology of the processed cross-section was observed. FIG. 12 is an SEM image obtained as a result of observing the cross-sectional morphology of the bonded sample 5 at a magnification of 5000 times. As a result of cross-sectional observation, voids were observed between the silver foil 17 and the silver plating layer 11 on the adherend surface. It is thought that adhesion failure occurred due to the small deposition area.

  According to the die-bonding sheet of Example 1, as shown in FIG. 6, the holes in the sheet are deformed while being crushed during crimping, and the sheet follows the adherend, whereby good adhesion can be obtained. I understood. On the other hand, when the dense silver foil 17 was used, the silver foil could not be greatly deformed at the time of pressure bonding, and voids were generated between the silver foil and the adherend, and an adhesive force could not be obtained.

(Examples 18 and 19 and Comparative Example 3)
(Production of die bond sheet)
Paste composition 1 was applied onto a polyimide sheet having a thickness of 50 μm using a metal film squeegee using a 125 μm thick PET film opened in a 20 × 20 mm ² square as a mask. The polyimide sheet coated with this paste-like composition 1 was placed on a hot plate, dried at 110 ° C. for 10 minutes and 180 ° C. for 10 minutes, and then covered with another polyimide sheet on the dried paste-like composition, Using a thermocompression bonding apparatus, the composition was cured at 300 ° C. for 10 minutes under the pressure conditions described in Table 4. The cured paste-like composition was peeled from the polyimide sheet and cut into 10 × 10 mm ² squares to obtain die bond sheets of Examples 18 and 19 and Comparative Example 3.

[Vacuum observation]
The porosity was measured by the following method. The die bond sheet was cut into a rectangle, the length and width of the die bond sheet were measured with a ruler, and the thickness was measured with a film thickness meter (ID-C112C, granite comparator stand, release, manufactured by Mitutoyo Corporation) to calculate the volume of the sheet. . The apparent density M ₁ (g / cm ³ ) of the die bond sheet was determined from the volume of the cut die bond sheet and the weight of the die bond sheet measured with a precision balance. And _{M 1} obtained by using the density _M 2 of the material constituting the die-bonding sheet (g / cm ^3), was determined porosity from the following equation (4).
Porosity (volume%) = [1- (M ₁ ) / (M ₂ )] × 100 (4)

Since the die-bonded sheets of Examples 1, 18, 19 and Comparative Example 3 use the paste-like composition 1 made of silver, M ₂ in the above formula (4) has a silver density of 10.5 g / cm ³ . Using this, the porosity (volume%) was determined. Since the die-bonding sheet of Example 9 uses the paste-like composition ₂ made of copper, the M ₂ in the above formula (4) uses a copper density of 8.96 g / cm ³ and uses a porosity (volume%). )

Regarding Examples 10 to 14 including the low melting point glass (density 5.5 g / cm ³ ), the density M ₂ of the material constituting the die bond sheet is calculated using the following formula (5), and M in the formula (4) _By substituting for ₂ , the porosity was determined.
M ₂ (g / cm ³ ) = 1 / [{(B / 100) /5.5} + {(1−B / 100) /10.5}] (5)
[B: Content of low melting point glass (mass%)]

The porosity of the die bond sheet after thermocompression bonding was measured by the following method. According to the method described in <Observation of cross-sectional morphology>, cross-sectional image data of 5000 times that of the die-bonded sheet after thermocompression bonding was obtained for the bonded sample. ImageJ was started up, the cross-sectional image data was opened, only the die bond sheet after thermocompression bonding was selected by dragging, and Image → Crop was selected to cut out the image. In the data of the die bond sheet after the cut out thermocompression bonding, Analyze → Measure was pressed, and the area (A ₁ ) of the entire image was measured. Next, selection was performed in the order of Image → Adjust → Threshold, and the binarization process was performed by adjusting the parameters so that only the holes were selected. Click Edit → Selection → Create Selection to confirm that the hole was selected, and then press Analyze → Measure to measure the area (A ₂ ) of the hole. The porosity after thermocompression bonding was obtained from the following formula (6).
Porosity after thermocompression bonding (volume%) = {(A ₂ ) / (A ₁ )} × 100 (6)

10 × 10 mm ² of the die bond sheets of Examples 18 and 19 and Comparative Example 3 were placed on a silver-plated copper plate (20 × 20 mm ² , thickness 2 mm) 18, and titanium, nickel and gold were plated in this order thereon. A silicon chip whose 5 × 5 mm ² adherent surface is gold-plated is placed, and an expanded graphite sheet of 6 × 6 mm ² is further placed thereon, and an atmosphere control thermocompression bonding apparatus (manufactured by Ayumi Industry) is used. Bonded samples 6 to 8 were obtained by treatment in air at 10 MPa and 300 ° C. for 10 minutes.

After the cross-sectional observation of the joined samples 6 to 8 is performed by casting and polishing by the method described in <Observation of cross-sectional morphology>, extra so that the outer shape of the cast sample falls within a range of width 20 mm × depth 12 mm × thickness 7 mm. This part was shaved with a polishing apparatus, and the casting resin on the silicon chip side was shaved down to the silicon chip. Then, the end part which came out of the mask was cut in the cross section polishing mode with an ion milling device under the conditions of an acceleration voltage of 6 kV, an argon gas flow rate of 0.07 to 0.1 cm ³ / min, and a processing time of 90 minutes, and a die bond layer The cross section was taken out. After the sputtering apparatus, SEM observation was performed according to the method described in <Observation of cross-sectional morphology>.

  FIG. 13 shows an SEM image of a die bond layer using the die bond sheet 8c of Example 19 produced under a pressure condition of 5 MPa, and FIG. 14 uses the die bond sheet 8d of Comparative Example 3 produced under a pressure condition of 10 MPa. 2 shows an SEM image of the die bond layer. When the die bond sheets of Examples 18 and 19 were used, the die bond sheet and the adherend adhered closely to each other without a gap, but when the die bond sheet of Comparative Example 3 was used, as shown in FIG. A gap was partially generated between the silver plating layer 19 and the adherend surface. This is presumably because the porosity in the die bond sheet was too low, so that the die bond sheet was not easily deformed at the time of pressure bonding, and as a result, film thickness unevenness and substrate irregularities could not be absorbed, leaving voids. Such voids are not preferable because they increase the local thermal resistance, decrease the adhesive force, and become a starting point of destruction due to thermal stress, thereby reducing the reliability of the device.

The die bond sheet of Example 15 is placed on a copper plate (19 × 25 mm ² , thickness 3 mm), an Au-plated Si chip (3 × 3 mm ² ) is placed thereon, and an alumina plate (4 × 4 mm ² , thickness 1 mm) is placed. Expanded graphite sheets (4 × 4 mm ² , thickness 0.5 mm) were stacked in this order. This was treated for 60 minutes under a formic acid-containing nitrogen atmosphere at 30 MPa and 385 ° C. with an atmosphere-controlled thermocompression bonding apparatus, and then treated with no pressure at 300 ° C. for 10 minutes for bonding to obtain a bonded sample 9. The processed cross section of the die bond sheet of Example 15 before thermocompression bonding and the bonded sample 9 were observed according to the method described in <Observation of Cross Section Morphology>. As a result of observing the cross-sectional morphology of the die bond sheet 20 of Example 15 before thermocompression bonding at 3000 times, the SEM image of FIG. 15 was obtained, and as a result of observing the processed cross section of the die bond sheet 21 of the bonding sample 9 at 3000 times, FIG. Sixteen SEM images were obtained. From FIGS. 15 and 16, it can be seen that the number of voids seen in the die bond sheet 20 before thermocompression is reduced by thermocompression.

  The die shear strength of the die bond sheets of Examples 1, 18, 19 and Comparative Example 3 was measured by the method described in [Measurement of die shear strength]. The die shear strength of the die bond sheets of Examples 9 and 15 to 17 is described in [Measurement of die shear strength] except that the die shear strength of the die bond sheets of Examples 10 to 14 was measured in a nitrogen atmosphere under the formic acid-containing nitrogen atmosphere. It measured by the method of. The results are shown in Table 4.

<Connection reliability test>
(Preparation of connection reliability test sample using Ag paste)
Mix 5.5 parts by mass of isobornylcyclohexanol (Telsolve MTPH, manufactured by Nippon Terpene) and 5.5 parts by mass of butyl stearate (manufactured by Wako Pure Chemical Industries, Ltd.) in a plastic bottle, seal and warm in a 50 ° C water bath. A clear and uniform solution was obtained while shaking. To this solution, 89 parts by mass of scaly silver particles (AgC239, manufactured by Fukuda Metal Foil Powder Industry) was added and stirred with a spatula until there was no dry powder. Further, the plastic bottle was sealed, and the mixture was stirred at 2000 rpm for 1 minute using a rotation / revolution type stirring device (Planetary Vacuum Mixer ARV-310, manufactured by Sinky Corporation) to obtain an Ag paste.

A metal mask having an opening of 5 × 9 mm ² was superimposed on a substrate (silver-plated copper plate 19 × 25 mm, thickness 3 mm), and Ag paste was printed using a metal squeegee. The substrate on which the Ag paste was printed was dried at 180 ° C. for 20 minutes using a clean oven (PVHC-210, manufactured by TABAIESPEC). Titanium, nickel, and gold are plated on the Ag paste in this order, and a 4 × 8 mm ² adherent surface is gold plated silicon chip, alumina plate (5 × 9 mm ² , thickness 1 mm), expanded graphite sheet (5 × 9 mm ² , thickness 0.5 mm) were stacked in this order, and bonded by processing for 10 minutes in air at 10 MPa and 300 ° C. using a thermocompression bonding apparatus. A primer (HIMAL, manufactured by Hitachi Chemical Co., Ltd.) is coated on the joined body, and this is sealed with a sealing material (CEL-420, manufactured by Hitachi Chemical Co., Ltd.), and a connection reliability test sample 1 using Ag paste is prepared. Produced.

(Preparation of Ag die bond sheet connection reliability test sample)
The Ag die bond sheet used in Example 1 was cut into 5 × 9 mm ² . On a substrate (silver plated copper plate 19 × 25 mm, thickness 3 mm), an Ag die bond sheet, titanium, nickel and gold are plated in this order, and a 4 × 8 mm ² adherent surface is a gold chip, an alumina plate, The expanded graphite sheets were stacked in this order, and bonded by treatment for 10 minutes under the conditions of 10 MPa and 300 ° C. in air using a thermocompression bonding apparatus. The joined body was coated with a primer and sealed with a sealing material to prepare a connection reliability test sample 2 using an Ag die bond sheet.

(Preparation of Cu die bond sheet connection reliability test sample)
The Cu die bond sheet used in Example 9 was cut into 5 × 9 mm ² . On a substrate (copper plate 19 × 25 mm, thickness 3 mm), a Cu die bond sheet, titanium, nickel and gold are plated in this order, and a 4 × 8 mm ² adherent surface is gold-plated silicon chip, alumina plate, expanded graphite The sheets are stacked in this order, and treated with an atmosphere-controlled thermocompression bonding apparatus (RF-100B, manufactured by Ayumi Kogyo Co., Ltd.) in a formic acid-containing nitrogen atmosphere at 10 MPa and 300 ° C. for 10 minutes, and then in nitrogen without pressure 300 ° C. 10 Minute processing and joining. The joined body was coated with a primer and sealed with a sealing material to prepare a connection reliability test sample 3 using a Cu die bond sheet.

(Connection reliability test)
The connection reliability test was performed at a low temperature side of −40 ° C., a high temperature side of 200 ° C., and a cycle of 30 minutes using a thermal shock test apparatus (TSA-72ES-W, manufactured by Tabay Espec). The connection reliability of the test sample was evaluated based on the ratio of the area where the die bond layer was peeled off after performing 200 cycles of the connection reliability test using ultrasonic tomography (InSight-300, manufactured by Insight). As a result, when using test sample 1 (Ag paste), 20 area%, when using test sample 2 (Ag die bond sheet), 20 area%, and when using test sample 3 (Cu die bond sheet), 0 area%. Area% peeling was observed. From the above results, the Ag die bond sheet had connection reliability equivalent to that of the Ag paste, and the Cu die bond sheet was superior in connection reliability to the Ag die bond sheet and the Ag die bond sheet.

DESCRIPTION OF SYMBOLS 1, 1a, 1b ... Die bond sheet, 2, 2a, 2b ... Semiconductor element, 3 ... Semiconductor element mounting support member, 4a, 4b ... Adhering surface, 5a, 5b ... Lead frame, 6 ... Wire, 7 ... Mold resin 8a, 8b, 8c, 8d ... die bond sheet (made of silver), 9 ... gold-plated silicon chip (coated gold), 10 ... copper layer of silver-plated alumina DCB substrate, 11 ... silver-plated layer of silver-plated alumina DCB substrate (the Chakumengin), 12 ... die bonding sheet (copper), 13 ... copper (the Chakumendo), 14 ... die bonding sheet (low-melting glass component containing), 15 ... surface oxidized Si substrate (adherend surface _SiO 2) 16 ... Aluminum substrate, 17 ... Silver foil, 18 ... Silver plated copper plate, 19 ... Silver plated layer of silver plated copper plate (silver to be deposited) 20 ... Copper die bond sheet (before thermocompression bonding), 21 ... Copper die bond sea (After thermal compression bonding).

Claims (4)

A porosity of 15 to 50% by volume, comprises silver and / or copper state, and are the carbon content of not more than 1.5 mass%, 0.06 to 13.6 atomic percent vanadium in terms of atom and tellurium A porous sheet containing 0.12 to 7.8 atomic% in terms of atoms is interposed between the semiconductor element and the semiconductor element mounting support member, and these are heated and pressurized to thereby provide the semiconductor element and the semiconductor element mounting. A method for manufacturing a semiconductor device, comprising joining a support member. A porosity of 15 to 50% by volume, comprises silver and / or copper state, and are the carbon content of not more than 1.5 mass%, 0.06 to 13.6 atomic percent vanadium in terms of atom and tellurium A die-bonding sheet comprising a porous sheet containing 0.12 to 7.8 atomic% in terms of atoms . The die bond sheet according to claim 2, wherein the porous sheet is obtained by forming a composition containing silver particles and / or copper particles and a dispersion medium into a sheet shape and heating the composition. . Through the die bonding sheet according to claim 2 or 3, wherein a and a semiconductor element and a support member for mounting a semiconductor element is bonded structure.