WO2021010171A1 - 接合フィルム、ウエハ加工用テープ、接合体の製造方法、接合体および貼合体 - Google Patents

接合フィルム、ウエハ加工用テープ、接合体の製造方法、接合体および貼合体 Download PDF

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WO2021010171A1
WO2021010171A1 PCT/JP2020/025904 JP2020025904W WO2021010171A1 WO 2021010171 A1 WO2021010171 A1 WO 2021010171A1 JP 2020025904 W JP2020025904 W JP 2020025904W WO 2021010171 A1 WO2021010171 A1 WO 2021010171A1
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Prior art keywords
fine particles
bonding
layer
metal fine
film
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PCT/JP2020/025904
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English (en)
French (fr)
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ノルザフリザ 新田
藤原 英道
佐藤 義浩
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古河電気工業株式会社
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Application filed by 古河電気工業株式会社 filed Critical 古河電気工業株式会社
Priority to CN202080047771.XA priority Critical patent/CN114051522B/zh
Priority to JP2021532775A priority patent/JP7354252B2/ja
Priority to EP20841520.8A priority patent/EP4001373A4/en
Publication of WO2021010171A1 publication Critical patent/WO2021010171A1/ja
Priority to US17/647,903 priority patent/US20220139864A1/en

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Definitions

  • the present invention relates to a bonding film and a wafer processing tape, and more particularly to a connecting film for connecting a semiconductor element and a substrate such as a circuit board or a ceramic substrate, and a wafer processing tape provided with the connection film.
  • a film-like adhesive (diatach film) has been used to bond a semiconductor chip to a wiring board or the like.
  • a dicing tape for fixing the semiconductor wafer when the semiconductor wafer is cut and separated (diced) into individual chips, and a die attach film (also referred to as a die bonding film) for adhering the cut semiconductor chip to a wiring substrate or the like.
  • a dicing / die bonding tape having the two functions of (referred to as) has been developed (see, for example, Patent Document 1).
  • solder is generally used for the connection between the power semiconductor element and the substrate.
  • cream solder obtained by adding flux to solder powder to have an appropriate viscosity is mainly used.
  • the surface of the semiconductor element may be contaminated, and there is a problem that a cleaning step is required.
  • lead-free solder material that does not contain lead.
  • Au-Sn-based solder is a lead-free solder material that can handle the heat generated by power semiconductors, but it is not practical because it is expensive.
  • Sn—Ag—Cu solder is an inexpensive solder material that is cheaper than Au—Sn solder, but there is a problem that the growth of intermetallic compounds due to thermal history leads to a decrease in reliability.
  • ACF anisotropic Conductive Film
  • thermosetting resin As a joining member that does not use solder, there is an anisotropic conductive film (Anisotropic Conductive Film: ACF) that is formed by mixing a thermosetting resin with fine metal particles having conductivity into a film.
  • ACF contains a certain proportion or more of resin in order to obtain a good adhesive state, the contact between metal particles becomes point contact, sufficient heat conduction cannot be expected, and the connection heat resistance is not sufficient. There was a point. Further, ACF is not suitable for connecting a power semiconductor having a large amount of heat generation because there is a concern that the thermosetting resin is deteriorated due to high heat.
  • metal paste a paste containing metal fine particles (hereinafter referred to as metal paste) (see, for example, Patent Document 2).
  • an organic dispersant that prevents condensation of metal fine particles during storage or manufacturing process and a dispersion auxiliary substance that reacts with the organic dispersant during bonding to remove the organic dispersant are added to the metal fine particles.
  • a solvent or the like is mixed with this to form a paste.
  • the metal fine particles include extremely fine particles having a particle size of at least about 1 to 500 nm, and the surface is in an active state.
  • the metal paste is applied to the bonding surface of the semiconductor element and / or the substrate by a dispenser or screen printing, and the temperature is 150 to 300 ° C. for a predetermined time (1 minute to 1 minute). Heat for about an hour).
  • the organic dispersant reacts with the dispersion auxiliary material to remove the organic dispersant, and at the same time, the solvent is also volatilized and removed.
  • the metal fine particles in the active state are bonded to each other to form a single film of the metal component.
  • the metal paste When applying the metal paste to the joint surface using a dispenser or screen printing, it is necessary to adjust the amount of solvent etc. to reduce the viscosity of the metal paste to some extent. However, if the viscosity is lowered, there is a problem that when the metal paste is applied to the joint surface, the metal paste scatters and adheres to a portion other than the joint surface of the semiconductor element or the substrate, contaminating the semiconductor element or the substrate. there were.
  • connection sheet in which a metal paste is formed into a sheet in advance has been proposed (see Patent Document 3).
  • the bonding layer itself has no adhesiveness, so that the bonding layer itself is not adhesive. It is necessary to place the bonding layer on the substrate using a tool or the like, and then mount the semiconductor element on the substrate to sinter the bonding layer. Therefore, there is a problem that the process becomes complicated.
  • Patent Document 4 a wafer processing tape that improves the adhesiveness problem of the bonding layer and simplifies the bonding process has been proposed (see Patent Document 4).
  • the wafer processing tape for joining the semiconductor element and the substrate described in Patent Document 4 is provided on the pressure-sensitive adhesive film and the pressure-sensitive adhesive film having the base material film and the pressure-sensitive adhesive layer provided on the base material film.
  • the conductive paste containing the metal fine particles (P) is characterized by having a conductive bonding layer formed into a film and a tack layer having tackiness and laminated on the conductive bonding layer. ..
  • JP-A-2010-265453 Japanese Unexamined Patent Publication No. 2006-352080 Japanese Unexamined Patent Publication No. 2013-236090 International Publication No. 2018/092671
  • the wafer processing tape described in Patent Document 4 has a problem that the types of semiconductor elements that can be bonded are limited by the types of metal fine particles constituting the conductive bonding layer. For example, when copper fine particles are used as metal fine particles, bonding to a copper electrode or gold electrode is considered to be good, and when silver fine particles are used as metal fine particles, bonding to a silver electrode or gold electrode is considered to be good. The types of layers and electrodes of semiconductor elements are limited.
  • a bonding film, a tape for wafer processing which has sufficient connection heat resistance and high reliability, has good bonding with a substrate regardless of the type of electrode of the semiconductor element, and has a simple bonding process. It is an object of the present invention to provide a method for producing a joint, a joint and a bonded body.
  • the bonding film according to the present invention is a bonding film for bonding a semiconductor element and a substrate, and is a conductive film in which a conductive paste containing metal fine particles (P) is formed into a film. It has a sex bonding layer and a tack layer having tack property and laminated on the conductive bonding layer, and the tack layer is a metal with respect to the metal fine particles (P) in the conductive bonding layer.
  • the metal fine particles (M) contain 0.1 to 1.0% by mass of the fine particles (M), and the metal fine particles (M) have a melting point of 250 ° C. or lower.
  • the average primary particle size of the metal fine particles (P) is preferably 10 to 500 nm.
  • the conductive paste contains an organic solvent (S).
  • the metal fine particles (P) contain copper or silver.
  • the conductive paste contains an organic binder (R).
  • the tack layer is selected from polyglycerin, glycerin fatty acid ester, polyglycerin fatty acid ester, phosphine, phosphites, sulfides, disulfides, trisulfides, and sulfoxides. It is preferably composed of one type or two or more types.
  • the metal fine particles (M) also have an average primary particle size of 1 to 3 ⁇ m.
  • the metal fine particles (M) contain tin.
  • the organic solvent (S) is an organic solvent (SC) composed of an alcohol having a boiling point of 100 ° C. or higher at normal pressure and having 1 or 2 or more hydroxyl groups in the molecule and / or a polyhydric alcohol. ) Is preferably included.
  • the organic binder (R) is a cellulose resin binder, an acetate resin binder, an acrylic resin binder, a urethane resin binder, a polyvinylpyrrolidone resin binder, a polyamide resin binder, and a butyral resin binder. , And one or more selected from the terpene binders.
  • the wafer processing tape according to the present invention includes an adhesive film having a base film and an adhesive layer provided on the base film, and any of the above. It has a bonding film, and is characterized in that a conductive bonding layer of the bonding film is provided on the pressure-sensitive adhesive layer.
  • the method for producing a bonded body according to the present invention has a tack property and a metal with a conductive bonding layer in which a conductive paste containing metal fine particles (P) is formed into a film.
  • a bonding film containing fine particles (M) and having a tack layer laminated on the conductive bonding layer is placed between a semiconductor element and a substrate and heated, the tack layer is thermally decomposed, and the metal fine particles are decomposed. It has a bonding step of bonding the semiconductor element and the substrate by sintering the metal fine particles (P) of the conductive bonding layer after the (M) melts and reacts with the electrodes of the semiconductor element. It is characterized by that.
  • the joint body of the semiconductor and the substrate according to the present invention has a conductive connecting member made of a porous metal body on the substrate, and the semiconductor and the substrate having a semiconductor element on the conductive connecting member. It is a bonded body and is bonded using the bonding film described in any of the above.
  • the metal porous body is a sintered body of metal fine particles (P) contained in the bonding film, and the metal.
  • the interface between the porous body and the electrode of the semiconductor element is characterized in that an alloy phase or a metal compound phase of the metal fine particles (M) contained in the bonding film and the electrode is formed.
  • the porosity of the metal porous body is preferably 1 to 6% by volume, and the average pore diameter is preferably 10 to 60 nm.
  • the bonded body according to the present invention is for bonding a base film, a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer provided on the base material film, a semiconductor element, and a substrate.
  • the bonding film is a bonded body in which the bonding film of the above and a semiconductor wafer are bonded, and the bonding film has a tack property with a conductive bonding layer in which a conductive paste containing metal fine particles (P) is formed into a film. It has a tack layer laminated on the conductive bonding layer, the conductive bonding layer is bonded to the pressure-sensitive adhesive layer, and the semiconductor wafer is bonded to the tack layer.
  • the layer is thermally decomposable and contains 0.1 to 1.0% by weight of the metal fine particles (M) with respect to the metal fine particles (P) in the conductive bonding layer, and is tacked by heating at the time of bonding.
  • the layer is thermally decomposed, the metal fine particles (M) are melted and reacted with the electrodes of the semiconductor element, and then the metal fine particles (P) of the conductive bonding layer are sintered, thereby causing the semiconductor element and the substrate. It is characterized in that and is joined.
  • a bonding film, a wafer processing tape which has sufficient connection heat resistance and high reliability, has good bonding with a substrate regardless of the type of electrode of the semiconductor element, and has a simple bonding process.
  • a method for producing a bonded body, a bonded body and a bonded body can be provided.
  • FIG. 1 is a cross-sectional view showing a wafer processing tape 10 according to an embodiment.
  • FIG. 2 is a diagram showing a state in which the semiconductor wafer 1 is bonded on the wafer processing tape 10.
  • FIG. 3 is a diagram for explaining a dicing process in a manufacturing process of a semiconductor device
  • FIG. 4 is a diagram for explaining an expanding process
  • FIG. 5 is a diagram for explaining a pickup process. Is.
  • FIG. 6 is a cross-sectional view schematically showing a semiconductor device manufactured by using the wafer processing tape according to the embodiment of the present invention.
  • the wafer processing tape 10 includes an adhesive film 12 composed of a base film 12a and an adhesive layer 12b formed on the base film 12a, and an adhesive film 12 on the adhesive film 12. It has a bonding film 13 laminated to the above.
  • the bonding film 13 has a conductive bonding layer 13a in which a conductive paste containing metal fine particles (P) is formed into a film, and a tack layer 13b having tack properties and laminated on the conductive bonding layer 13a.
  • a conductive bonding layer 13a is provided on the pressure-sensitive adhesive layer 12b.
  • the wafer processing tape 10 includes a dicing step of cutting a semiconductor wafer 1 into a semiconductor element 2 (also referred to as a chip or a semiconductor chip) and a substrate 40 such as a circuit board, a ceramic substrate, and a lead frame from the cut semiconductor element 2 (FIG. It is used in both the die bonding step and the die bonding step of joining (see 6). The dicing process will be described later with reference to FIG.
  • the pressure-sensitive adhesive layer 12b may be composed of one layer of pressure-sensitive adhesive layer, or may be composed of two or more layers of pressure-sensitive adhesive layer laminated. Note that FIG. 1 shows how the release film 11 is provided on the wafer processing tape 10 in order to protect the bonding film 13. As the release film 11, a known one can be used.
  • the adhesive film 12 and the bonding film 13 may be formed in a predetermined shape in advance according to the process of use and the apparatus.
  • the bonding film 13 is peeled off from the adhesive film 12 and adhered to the semiconductor element 2 to be picked up when the semiconductor wafer 1 is bonded and diced and then the semiconductor element 2 is picked up. It is used as a bonding material when fixing 2 to the substrate 40. Therefore, the bonding film 13 has adhesiveness and peelability that can be peeled off from the adhesive film 12 in a state of being attached to the fragmented semiconductor element 2 in the pick-up process, and further, the semiconductor element 2
  • the substrate 40 is bonded to the substrate 40 to have sufficient bonding reliability. The pickup process will be described later with reference to FIG.
  • the bonding film 13 has a conductive bonding layer 13a in which a conductive paste containing metal fine particles (P) is formed into a film, and a tack layer 13b having tack properties and laminated on the conductive bonding layer 13a.
  • the tack property means the adhesive property, and specifically, the adhesive property that allows the conductive bonding layer 13a to be held by the semiconductor wafer 1 or the semiconductor element 2.
  • the conductive paste preferably contains an organic dispersion medium (D) in addition to containing metal fine particles (P).
  • the metal fine particles (P) contained in the conductive paste include copper, magnesium, aluminum, zinc, gallium, titanium, manganese, germanium, silver, gold, nickel, and platinum.
  • one kind of fine particles selected from the metal element group consisting of palladium fine particles obtained by mixing two or more kinds selected from the metal element group, fine particles made of an alloy of two or more elements selected from the metal element group, the metal.
  • the metal fine particles (P) are (i) copper fine particles (P1) or (ii) copper fine particles (P1) 90 to 100% by mass, and magnesium and aluminum in consideration of conductivity and sinterability during heat treatment. , Zinc, gallium, titanium, manganese, and 2 or more kinds of second metal fine particles (P2) selected from germanium, 10 to 0% by mass, are preferably used.
  • the copper fine particles (P1) are metals having a relatively high conductivity, while the metal fine particles (P2) are metals having a relatively low melting point. When the second metal fine particles (P2) are used in combination with the copper fine particles (P1), the metal fine particles (P2) form an alloy with the copper fine particles (P1) in the metal fine particles (P), or the metal.
  • the fine particles (P2) form a coating layer on the surface of the copper fine particles (P1) in the metal fine particles (P).
  • the heat treatment temperature can be lowered and the bonding between the metal fine particles can be facilitated.
  • the average primary particle size of the metal fine particles (P) before the heat treatment is preferably 10 to 500 nm, more preferably 30 to 300 nm, and even more preferably 100 to 150 nm. If the average primary particle size of the metal fine particles (P) is less than 10 nm, it may be difficult to form uniform particle size and pores throughout the sintered body by heat treatment (sintering), and the thermal cycle The characteristics may be reduced, and the bonding strength may also be reduced. On the other hand, when the average primary particle size exceeds 500 nm, the metal fine particles and the pore diameters constituting the sintered body become close to the micron size, and the thermal cycle characteristics also deteriorate.
  • the average primary particle size of the metal fine particles (P) before the heat treatment can be measured by a scanning electron microscope (SEM). For example, if the two-dimensional shape is approximately circular, the diameter of the circle, if it is approximately elliptical, the minor axis of the ellipse, if it is approximately square, the length of the side of the square, approximately rectangular. If so, measure the length of the short side of the rectangle.
  • the "average primary particle size" is obtained by observing and measuring the particle size of a plurality of randomly selected 10 to 20 particles with the above-mentioned microscope and calculating the average value thereof.
  • the method for producing the metal fine particles (P) is not particularly limited, and for example, a wet chemical reduction method, an atomizing method, a plating method, a plasma CVD method, a MOCVD method, or the like can be used.
  • metal fine particles (P) having an average primary particle size of 10 to 500 nm As a method for producing metal fine particles (P) having an average primary particle size of 10 to 500 nm, the method disclosed in Japanese Patent Application Laid-Open No. 2008-231564 can be adopted.
  • the production method disclosed in the publication it is possible to easily obtain metal fine particles (P) having an average primary particle size of 10 to 500 nm, and in the production method of the metal fine particles disclosed in the publication, After the reduction reaction of the metal ions is completed, an organic dispersion medium (D) is added to the metal fine particles from which impurities in the reaction solution have been removed, which is recovered by adding a flocculant to the reduction reaction aqueous solution and centrifugation or the like, and kneading. , The conductive paste of the present invention can be produced.
  • the organic dispersion medium (D) disperses the metal fine particles (P) in the conductive paste, adjusts the viscosity of the conductive paste, maintains the film shape, and reduces in liquid and gaseous form during heat treatment. It can exert its function as an agent.
  • the organic dispersion medium (D) preferably contains at least an organic solvent (S) and further contains an organic binder (R).
  • the organic solvent (S) preferably contains an organic solvent (SC) consisting of an alcohol having a boiling point of 100 ° C. or higher at normal pressure and having 1 or 2 or more hydroxyl groups in the molecule and / or a polyhydric alcohol. Further, the organic solvent (S) is (i) at least 5 to 90% by volume of the organic solvent (SA) having an amide group, and the low boiling point organic solvent (SB) 5 having a boiling point of 20 to 100 ° C. at normal pressure. Organic solvent (SC) containing 5 to 90% by volume of an organic solvent (SC) consisting of an alcohol having a boiling point of 100 ° C. or higher at normal pressure and having 1 or 2 or more hydroxyl groups in the molecule and / or a polyhydric alcohol.
  • SC organic solvent
  • the solvent (S1), and (ii) at least an organic solvent (SA) having an amide group of 5 to 95% by volume, and having a boiling point of 100 ° C. or higher at normal pressure and having 1 or 2 or more hydroxyl groups in the molecule. It is preferably one selected from the organic solvent (S2) containing 5 to 95% by volume of the organic solvent (SC) composed of alcohol and / or polyhydric alcohol.
  • SA organic solvent
  • SC organic solvent
  • polar organic solvents such as tetrahydrofuran, jigglime, ethylene carbonate, propylene carbonate, sulfolane, and dimethyl sulfoxide can be used.
  • the organic solvent (S1) is at least 5 to 90% by volume of the organic solvent (SA) having an amide group, 5 to 45% by volume of a low boiling point organic solvent (SB) having a boiling point of 20 to 100 ° C. at normal pressure, and It is an organic solvent having a boiling point of 100 ° C. or higher at normal pressure and containing 5 to 90% by volume of an organic solvent (SC) composed of an alcohol having 1 or 2 or more hydroxyl groups in the molecule and / or a polyhydric alcohol.
  • SA organic solvent
  • the organic solvent (SA) is contained in the organic solvent (S1) in an amount of 5 to 90% by volume to improve dispersibility and storage stability in the conductive paste, and further heat-treat the conductive bonding layer on the bonding surface.
  • the organic solvent (SB) is an organic solvent of metal fine particles (P) which is contained in the organic solvent (S1) in an amount of 5 to 45% by volume or more, reduces the interaction between solvent molecules in the conductive paste, and is dispersed. It has an action of improving the affinity for (S1).
  • the organic solvent (SC) is contained in the organic solvent (S1) in an amount of 5 to 90% by volume or more, and it becomes possible to achieve further long-term stabilization of dispersibility and dispersibility in the conductive paste.
  • the organic solvent (S1) is an organic solvent containing at least 5 to 90% by volume of the organic solvent (SA), 5 to 45% by volume of the organic solvent (SB), and 5 to 90% by volume of the organic solvent (SC)."
  • the organic solvent (S1) may be blended from the organic solvent (SA), the organic solvent (SB), and the organic solvent (SC) so as to have a blending ratio of 100% by volume, or the blending ratio.
  • the organic solvent (SA), the organic solvent (SB), and the organic solvent It is preferable that the component composed of (SC) is contained in an amount of 90% by volume or more, and more preferably 95% by volume or more.
  • the blending ratio is preferably 5 to 70% by volume of the organic solvent (SA), 5 to 30% by volume of the organic solvent (SB), and 10 to 90% by volume of the organic solvent (SC).
  • the organic solvent (S2) includes at least 5 to 95% by volume of the organic solvent (SA) having an amide group, and an alcohol having a boiling point of 100 ° C. or higher at normal pressure and having 1 or 2 or more hydroxyl groups in the molecule. / Or an organic solvent containing 5 to 95% by volume of an organic solvent (SC) composed of a polyhydric alcohol.
  • SA organic solvent
  • SC organic solvent
  • the organic solvent (SA) is contained in the organic solvent (S2) in an amount of 5 to 95% by volume, the dispersibility and storage stability are improved in the mixed organic solvent, and the conductive paste is heat-treated to make the metal porous. It has the effect of improving the adhesion at the joint surface when forming the body.
  • the organic solvent (SC) is contained in the organic solvent (S2) in an amount of 5 to 95% by volume, further improving the dispersibility in the conductive paste. Further, when the organic solvent (SA) and the organic solvent (SC) are present in the organic solvent (S2), even at a relatively low heat treatment temperature when the conductive bonding layer is placed on the bonding surface and then heat-treated. Sintering can proceed.
  • the organic solvent (S2) is an organic solvent containing at least 5 to 95% by volume of the organic solvent (SA) and 5 to 95% by volume of the organic solvent (SC).
  • the organic solvent (S2) is an organic solvent.
  • SA and the organic solvent (SC) may be blended so as to be 100% by volume in the blending ratio, and other within the blending ratio and within the range not impairing the effect of the present invention.
  • an organic solvent component may be blended, but in this case, the component composed of the organic solvent (SA) and the organic solvent (SC) is preferably contained in an amount of 90% by volume or more, more preferably 95% by volume or more. preferable.
  • the blending ratio is preferably 5 to 80% by volume of the organic solvent (SA) and 10 to 90% by volume of the organic solvent (SC).
  • organic solvent SC
  • SA organic solvent
  • SB organic solvent
  • the organic solvent (SC) is a reducing organic compound consisting of an alcohol having a boiling point of 100 ° C. or higher at normal pressure and having 1 or 2 or more hydroxyl groups in the molecule and / or a polyhydric alcohol. Further, alcohols having 5 or more carbon atoms and polyhydric alcohols having 2 or more carbon atoms are preferable, and those which are liquid at room temperature and have a high relative permittivity, for example, those having 10 or more carbon atoms are preferable. Since metal fine particles (P) having an average primary particle size of 10 to 500 nm have a large surface area, it is necessary to consider the influence of oxidation, but the organic solvents (SC) listed below are liquid during heat treatment (sintering).
  • organic solvent (SC) include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and the like.
  • sugar alcohols such as threitol, erythritol, pentaerythritol, pentatol, and hexitol can also be used.
  • pentitol includes Xyritol, Ribitol, and Arabitol.
  • the hexitol includes mannitol, sorbitol, dulcitol and the like.
  • glycerol aldehyde (Glyceric aldehyde), dioxy-acetone, treose, erythrulus, erythrose, arabinose, ribose, ribose, ribose, ribose.
  • SC organic solvents
  • polyhydric alcohols having two or more hydroxyl groups in the molecule are more preferable, and ethylene glycol and glycerol are particularly preferable.
  • the organic solvent (SA) is a compound having an amide group (-CONH-), and a compound having a particularly high relative permittivity is preferable.
  • N-methylacetamide, N-methylformamide, N-methylpropanamide, formamide and the like which have a relative permittivity of 100 or more at a measurement temperature of 20 to 32 ° C.
  • the measurement temperature range of 20 to 32 ° C. corresponds to the paste formation and film formation processing temperatures, and the relative permittivity at that time is 100 or more, so that the metal fine particles (P) in the paste formation step before film formation.
  • P metal fine particles
  • the organic solvent (SB) is an organic compound having a boiling point at normal pressure in the range of 20 to 100 ° C, preferably 60.0 to 100 ° C. If the boiling point at normal pressure is less than 20 ° C., the components of the organic solvent (SB) may volatilize and the paste composition may change when the particle dispersion containing the organic solvent (SB) is stored at room temperature. .. Further, when the boiling point at normal pressure is 100 ° C. or lower, it can be expected that the effect of reducing the mutual attractive force between the solvent molecules due to the addition of the solvent and further improving the dispersibility of the fine particles is effectively exhibited. Further, when the boiling point at normal pressure is 60 ° C.
  • an organic solvent SB
  • an ether compound SB1 represented by the general formula R1-O-R2 (R1 and R2 are independently alkyl groups and have 1 to 4 carbon atoms)
  • generally Alcohol SB2 represented by the formula R3-OH (R3 is an alkyl group and has 1 to 4 carbon atoms)
  • the general formula R4-C O) -R5 (R4 and R5 are respectively).
  • the ketone compound (SB3) which is an independently alkyl group and has 1 to 2 carbon atoms
  • the general formula R6- (N-R7) -R8 R6, R7, R8 are independent of each other.
  • An amine-based compound (SB4) represented by an alkyl group or a hydrogen atom having a carbon atom number of 0 to 2) can be exemplified.
  • the above organic solvent (SB) is illustrated below, but the number in parentheses after the compound name indicates the boiling point at normal pressure.
  • the ether-based compound (SB1) include diethyl ether (35 ° C.), methylpropyl ether (31 ° C.), dipropyl ether (89 ° C.), diisopropyl ether (68 ° C.), and methyl-t-butyl ether (55.3 ° C.). ), T-amylmethyl ether (85 ° C.), divinyl ether (28.5 ° C.), ethyl vinyl ether (36 ° C.), allyl ether (94 ° C.) and the like.
  • Examples of the alcohol (SB2) include methanol (64.7 ° C), ethanol (78.0 ° C), 1-propanol (97.15 ° C), 2-propanol (82.4 ° C), and 2-butanol (100 ° C). ), 2-Methyl 2-propanol (83 ° C.) and the like.
  • Examples of the ketone compound (SB3) include acetone (56.5 ° C.), methyl ethyl ketone (79.5 ° C.), diethylentanone (100 ° C.) and the like.
  • examples of the amine compound (SB4) include triethylamine (89.7 ° C.) and diethylamine (55.5 ° C.).
  • the organic binder (R) exerts a function of suppressing aggregation of metal fine particles (P) in the conductive paste, adjusting the viscosity of the conductive paste, and maintaining the shape of the conductive connecting member precursor.
  • the organic binder (R) is included in a cellulose resin binder, an acetate resin binder, an acrylic resin binder, a urethane resin binder, a polyvinylpyrrolidone resin binder, a polyamide resin binder, a butyral resin binder, and a terpene binder.
  • a cellulose resin binder an acetate resin binder, an acrylic resin binder, a urethane resin binder, a polyvinylpyrrolidone resin binder, a polyamide resin binder, a butyral resin binder, and a terpene binder.
  • One or more selected from the above is preferable.
  • the cellulose resin binders are acetyl cellulose, methyl cellulose, ethyl cellulose, butyl cellulose, and nitro cellulose;
  • the acetate resin binders are methyl glycol acetate, ethyl glycol acetate, butyl glycol acetate, ethyl diglycol acetate, and butyl di.
  • Acrylic resin binders are methyl methacrylate, ethyl methacrylate, and butyl methacrylate; Urethane resin binders are 2,4-tolylene diisocyanate, and p-phenylenedi isocyanate;
  • Polyvinylpyrrolidone resin binders are polyvinylpyrrolidone, and N-vinyl. Pyrrolidone; polyamide resin binders are polyamide 6, polyamide 66, and polyamide 11; butyral resin binders are polyvinyl butyral; terpene binders are one or more selected from pinen, cineol, limonene, and terpineol. Is preferable.
  • the conductive paste is a conductive paste containing metal fine particles (P) and an organic dispersion medium (D) composed of an organic solvent (S), or the metal fine particles (P), an organic solvent (S), and an organic binder. It is a conductive paste containing an organic dispersion medium (D) made of (R). When this is heat-treated, when a certain temperature is reached, the evaporation of the organic solvent (S) or the evaporation of the organic solvent (S) and the thermal decomposition of the organic binder (R) proceed, and the surface of the metal fine particles (P) appears. , It functions as a bonding material by utilizing the principle of bonding (sintering) to each other on the surface.
  • the mixing ratio (P / D) of the metal fine particles (P) and the organic dispersion medium (D) in the conductive paste is 50 to 85% by mass / 50 to 15% by mass (the total of mass% is 100% by mass). Is preferable.
  • metal fine particles other than the above, an organic dispersion medium, and the like can be added to the conductive paste of the present invention as long as the effects of the present invention are not impaired.
  • the blending ratio of the metal fine particles (P) exceeds 85% by mass, the paste becomes highly viscous, and there is a risk that the bond between the surfaces of the metal fine particles (P) will be insufficient in the heat treatment and the conductivity will decrease.
  • the mixing ratio of the metal fine particles (P) is less than 50% by mass, the viscosity of the paste is lowered, it becomes difficult to maintain the film shape, and there is a possibility that a problem of shrinkage may occur during the heat treatment, and further, heating There may be a disadvantage that the evaporation rate of the organic dispersion medium (D) becomes slow during the treatment.
  • the blending ratio (P / D) of the metal fine particles (P) and the organic dispersion medium (D) is more preferably 55 to 80% by mass / 45 to 20% by mass.
  • the blending ratio (S / R) of the organic solvent (S) and the organic binder (R) in the organic dispersion medium (D) is 80 to 100% by mass / 20 to 0% by mass (the total of mass% is any). Is also preferably 100% by mass), and more preferably 85 to 95% by mass / 15 to 5% by mass.
  • the blending ratio of the organic binder (R) in the organic dispersion medium (D) exceeds 20% by mass, the rate at which the organic binder (R) is thermally decomposed and scattered when the conductive bonding layer 13a is heat-treated becomes slow. Further, if the amount of residual carbon in the conductive connecting member increases, sintering is hindered, which may cause problems such as cracking and peeling, which is not preferable.
  • the organic solvent (S) is selected, the metal fine particles (P) can be uniformly dispersed only with the solvent, the viscosity of the conductive paste can be adjusted, and the film shape can be maintained.
  • D a component consisting of only the organic solvent (S) can be used.
  • additives such as defoamers, dispersants, plasticizers, surfactants, and thickeners can be added to the conductive paste as needed.
  • each component can be mixed and then kneaded using a ball mill or the like.
  • the tack layer 13b is for holding the conductive bonding layer 13a on the semiconductor wafer 1 and the semiconductor element 2, and has tack property. Further, the tack layer 13b is thermally decomposed by heating when the semiconductor element 2 and the substrate 40 are joined.
  • the tack layer 13b is not particularly limited as long as it has such properties, and may be composed of any material.
  • the tack layer 13b Since the tack layer 13b has no tack property in the conductive bonding layer 13a, it is a layer for improving the adhesiveness between the semiconductor wafer 1 or the semiconductor element 2 and the conductive bonding layer 13a. Without the tack layer 13b, the adhesive force between the semiconductor wafer 1 or the semiconductor element 2 and the conductive bonding layer 13a is weak, so that the semiconductor wafer 1 or the semiconductor element 2 and the semiconductor wafer 1 or the semiconductor element 2 are used when dicing the semiconductor wafer 1 or picking up the semiconductor element 2. It peels off from the conductive bonding layer 13a. Further, the tack layer 13b is also a layer for increasing the adhesion of the conductive bonding layer 13a to the semiconductor wafer 1 and the semiconductor element 2. By increasing the adhesion, the bonding strength when the semiconductor element 2 and the substrate 40 are bonded via the conductive bonding layer 13a is also improved.
  • the tack layer 13b is thermally decomposed by heating when the semiconductor element 2 and the substrate 40 are bonded, so that the semiconductor element 2 and the substrate 40 are mechanically bonded via the conductive bonding layer 13a. It is important to be done. Therefore, the weight reduction of the tack layer 13b at the heating temperature at the time of joining is preferably 70% by weight or more, more preferably 85% by weight in the thermogravimetric measurement at a heating rate of 5 ° C./min under an air atmosphere. Above, more preferably 95% by weight or more.
  • the tack layer 13b is in direct contact with the semiconductor element 2 at the time of joining, the effect of activating the surface of the electrode of the semiconductor element 2 is also expected. It is considered that this is because when the substance contained in the tack layer 13b decomposes during heating, it reacts with the oxide layer on the surface of the electrode, which is a metal, to clean the metal surface. By activating the surface of the electrode of the semiconductor element 2 in this way, the adhesion between the electrode of the semiconductor element 2 and the conductive bonding layer 13a can be improved.
  • the material constituting the tack layer 13b it is preferable to use a material that does not dissolve in a polar or non-polar solvent at room temperature but easily dissolves when heated to the melting point. Such a material is heated to a melting point, dissolved in a solvent, coated on a conductive bonding layer 13a or the like, cooled to room temperature, and the solvent is evaporated to form a film-like body having tackiness. Can be done.
  • the solvent a known solvent can be appropriately used, but it is preferable to use a solvent having a low boiling point in order to facilitate evaporation during film formation. An organic solvent (SB) can also be used as the low boiling point solvent.
  • the tack layer 13b is composed of a substance that reduces the metal fine particles (P) when the metal fine particles (P) in the conductive paste are heat-sintered.
  • the reaction temperature region is wide and the metal fine particles (P) are reduced, which lowers the resistivity of the metal fine particles (P) after sintering and improves the conductivity. ..
  • the tack layer 13b includes, for example, polyglycerin (melting point: 23 ° C.); glycerin monocaplate (melting point: 46 ° C.), glycerin monolaurate (melting point: 57 ° C.), glycerin monostearate (melting point: 70 ° C.), glycerin monobe.
  • Glycerin fatty acid ester such as henate (melting point: 85 ° C.); Polyglycerin fatty acid ester such as diglycerin stearate (melting point: 61 ° C.), diglycerin laurate (melting point: 34 ° C.); styrene p-styryldiphenylphosphine (melting point: melting point) : 75 ° C.), Triphenylphosphine (melting point: 81 ° C.), Tri-n-octylphosphine (melting point: 30 ° C.) and other phosphinides; phosphites; bis (4-methacryloylthiophenyl) sulfide (melting point: 64 ° C.) ), Phenyl p-tolyl sulfide (melting point: 23 ° C.), flufuryl sulfide (melting point: 32 ° C.) and other sul
  • the tack layer 13b does not hinder the tack property and the thermal decomposability, and is a defoaming agent and dispersed as necessary within a range in which there is no problem in terms of contamination of the semiconductor element 2 and the substrate 40 and generation of bumping gas.
  • Known additives such as agents, plasticizers, surfactants and thickeners can be added.
  • the tack layer 13b contains 0.1 to 1.0% by mass of metal fine particles (M) (also referred to as “metal fine particles in the tack layer”) with respect to the metal fine particles (P) in the conductive bonding layer 13a. ..
  • the metal fine particles (M) have a melting point of 250 ° C. or lower.
  • the metal fine particles (M) are preferably tin or alloy fine particles thereof, and for example, Sn solder powder, SnNiCu, SnNiCu (Ge), SnAgCu, SnAu powder, and the like can be used.
  • the tack layer 13b By adding metal fine particles (M) to the tack layer 13b in an amount of 0.1 to 1.0% by mass based on the metal fine particles (P) in the conductive bonding layer 13a, the tack layer 13b is heated by the heat at the time of bonding.
  • the conductive bonding layer 13a and the semiconductor element 2 The bondability with the electrode is improved, and good bonding can be performed regardless of the type of the metal fine particles (P) constituting the conductive bonding layer 13a and the type of the electrode.
  • the average primary particle size of the metal fine particles (M) is preferably 1 to 3 ⁇ m, and more preferably 1 to 2 ⁇ m in order to further reduce the thickness of the diffusion phase to be formed.
  • the average primary particle size of the metal fine particles (M) is less than 1 ⁇ m, sintering starts from a low temperature due to the size effect, the particle size becomes large or the particle size varies from the initial stage of sintering, and the diffusion reaction with the electrode is poor. However, there is a risk that the diffusion phase will vary. Further, if the average primary particle size exceeds 3 ⁇ m, the diffusion phase due to the diffusion reaction may be thickened, which may hinder the conductivity and heat dissipation of the bonded body.
  • the average primary particle size of the metal fine particles (M) can be measured by a scanning electron microscope (SEM). For example, if the two-dimensional shape is approximately circular, the diameter of the circle, if it is approximately elliptical, the minor axis of the ellipse, if it is approximately square, the length of the side of the square, approximately rectangular. If so, measure the length of the short side of the rectangle.
  • SEM scanning electron microscope
  • the "average primary particle size” is obtained by observing and measuring the particle size of a plurality of randomly selected 10 to 20 particles with the above-mentioned microscope and calculating the average value thereof.
  • the release film is placed on the mounting table, and the spacer is placed on the release film.
  • the spacer is, for example, a metal plate such as SUS, and has a circular opening in the center.
  • the above-mentioned conductive paste is placed on the release film, which is the opening of the spacer, and screen printing is performed using a squeegee to uniformly roll the conductive paste, whereby the conductive paste is a circular film. It becomes a shape.
  • the release film and the spacer are removed.
  • the conductive bonding layer 13a is formed by pre-drying the conductive paste formed into a circular film.
  • the time for pre-drying depends on the print thickness, but can be set to, for example, 5 to 20 minutes.
  • the material of the constituent component of the tack layer 13b is heated, kneaded in a solvent, applied on the conductive bonding layer 13a by a squeegee method, a spray coating method, or the like, and cooled. Then, the tack layer 13b is formed by heating and drying to evaporate the solvent.
  • the bonding film 13 of the present invention is provided on the adhesive film 12 to form the wafer processing tape 10 as a whole, but the bonding film 13 is bonded as a material for producing the wafer processing tape 10.
  • the film 13 may be traded alone, in which case it is preferable that both sides of the bonded film 13 are protected by a protective film.
  • a protective film a known film such as polyethylene-based, polystyrene-based, polyethylene terephthalate (PET) -based, or a film that has been subjected to a mold release treatment can be used, but a hard film suitable for holding the bonded film 13 can be used. It is preferable to use a polyethylene film or a polystyrene film from the viewpoint of having a shaving.
  • the thickness of the protective film is not particularly limited and may be set as appropriate, but is preferably 10 to 300 ⁇ m.
  • the adhesive film 12 has sufficient adhesive strength so that the semiconductor wafer 1 held by the bonding film 13 does not peel off when dicing the semiconductor wafer 1, and picks up the semiconductor element 2 that has been separated after dicing. In some cases, it has a low adhesive strength so that it can be easily peeled off from the bonding film 13.
  • the pressure-sensitive adhesive film 12 exemplifies a base film 12a provided with a pressure-sensitive adhesive layer 12b, but the present invention is not limited to this, and is used as a dicing tape. A known adhesive film can be used.
  • the base film 12a of the pressure-sensitive adhesive film 12 any conventionally known base film 12a can be used without particular limitation, but as will be described later, in the present embodiment, the pressure-sensitive adhesive layer 12b is energy-curable. Since a radiation-curable material is used among the materials of the above, a material having radiation permeability is used.
  • the base film 12a may be a mixture of two or more kinds of materials selected from these groups, or may be a single layer or a multi-layered one.
  • the thickness of the base film 12a is not particularly limited and may be set as appropriate, but is preferably 50 to 200 ⁇ m.
  • the pressure-sensitive adhesive layer 12b is cured by irradiating the pressure-sensitive adhesive film 12 with radiation such as ultraviolet rays, and the pressure-sensitive adhesive layer 12b is easily peeled off from the bonding film 13. Therefore, the pressure-sensitive adhesive layer 12b Resins include known chlorinated polypropylene resin, acrylic resin, polyester resin, polyurethane resin, epoxy resin, addition reaction type organopolysiloxane resin, silicon acrylate resin, ethylene-vinyl acetate copolymer used for adhesives.
  • Ethylene-ethyl acrylate copolymer ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, various elastomers such as polyisoprene, styrene-butadiene copolymer and hydrogenated products thereof, and mixtures thereof.
  • a radiopolymerizable compound it is preferable to appropriately blend a radiopolymerizable compound to prepare a pressure-sensitive adhesive.
  • various surfactants and surface smoothing agents may be added.
  • the thickness of the pressure-sensitive adhesive layer 12b is not particularly limited and may be set as appropriate, but is preferably 5 to 30 ⁇ m.
  • radiopolymerizable compound examples include a low molecular weight compound having at least two photopolymerizable carbon-carbon double bonds in a molecule that can be three-dimensionally networked by light irradiation, and a photopolymerizable carbon-carbon double bond group.
  • Polymers and oligomers having a substituent are used. Specifically, trimethylolpropan triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butylene glycol diacrylate, 1,6 hexanediol di. Acrylate, polyethylene glycol diacrylate, oligoester acrylate, silicon acrylate, and other copolymers of acrylic acid and various acrylic acid esters can be applied.
  • Urethane acrylate-based oligomers include polyol compounds such as polyester type or polyether type and polyvalent isocyanate compounds (for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene).
  • polyol compounds such as polyester type or polyether type
  • polyvalent isocyanate compounds for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene.
  • An acrylate or methacrylate having a hydroxyl group for example, 2-hydroxyethyl
  • the pressure-sensitive adhesive layer 12b may be a mixture of two or more kinds selected from the above resins.
  • composition of the pressure-sensitive adhesive layer 12b a composition in which an acrylic pressure-sensitive adhesive, a photopolymerization initiator, a curing agent, etc. are appropriately blended can be used in addition to a radiation-polymerizable compound that is cured by irradiation with radiation.
  • a photopolymerization initiator for example, isopropylbenzoin ether, isobutylbenzoin ether, benzophenone, Michler's ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, benzyldimethylketal, ⁇ -hydroxycyclohexylphenylketone, 2-hydroxymethylphenyl.
  • Propane or the like can be used.
  • the blending amount of these photopolymerization initiators is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the acrylic copolymer.
  • the adhesive film 12 can be produced by a conventionally known method as a method for producing a dicing tape.
  • the wafer processing tape 10 can be manufactured by laminating the conductive bonding layer 13a of the conductive bonding layer 13 described above on the pressure-sensitive adhesive layer 12b of the adhesive film 12.
  • FIG. 2 shows a state in which the semiconductor wafer 1 and the ring frame 20 are bonded to the wafer processing tape 10.
  • the adhesive layer 12b of the adhesive film 12 is attached to the ring frame 20, and the semiconductor wafer 1 is attached to the tack layer 13b of the bonding film 13.
  • the bonding order is not limited, and the adhesive layer 12b of the adhesive film 12 may be attached to the ring frame 20 after the semiconductor wafer 1 is attached to the bonding film 13. Further, the adhesive film 12 may be attached to the ring frame 20 and the semiconductor wafer 1 may be attached to the bonding film 13 at the same time.
  • a dicing step of the semiconductor wafer 1 is carried out, and then a step of irradiating the adhesive film 12 with energy rays, for example, ultraviolet rays is carried out.
  • energy rays for example, ultraviolet rays
  • the wafer processing tape 10 is suction-supported from the adhesive film 12 surface side by the suction stage 22.
  • the semiconductor wafer 1 and the bonding film 13 are cut into two semiconductor elements by the dicing blade 21 to be individualized, and then energy rays are irradiated from the lower surface side of the adhesive film 12.
  • the pressure-sensitive adhesive layer 12b is cured and its adhesive strength is reduced.
  • the adhesive force of the adhesive layer 12b of the adhesive film 12 may be reduced by an external stimulus such as heating.
  • the pressure-sensitive adhesive layer 12b is composed of two or more pressure-sensitive adhesive layers, one or all of the pressure-sensitive adhesive layers are cured by energy ray irradiation, and one layer in each pressure-sensitive adhesive layer is cured. Alternatively, the adhesive strength of all layers may be reduced.
  • an expanding step is carried out in which the adhesive film 12 holding the diced semiconductor element 2 and the bonding film 13 is stretched in the circumferential direction of the ring frame 20.
  • the hollow cylindrical push-up member 30 is raised from the lower surface side of the adhesive film 12 with respect to the adhesive film 12 holding the plurality of diced semiconductor elements 2 and the bonding film 13, and the adhesive film. 12 is stretched in the circumferential direction of the ring frame 20.
  • the pick-up step of picking up the semiconductor element 2 is carried out with the adhesive film 12 in the expanded state.
  • the semiconductor element 2 is individualized by pushing up the semiconductor element 2 from the lower surface side of the adhesive film 12 with a pin 31 and adsorbing the semiconductor element 2 from the upper surface side of the adhesive film 12 with an adsorption jig 32. Is picked up together with the bonding film 13.
  • the joining process is carried out. Specifically, the conductive bonding layer 13a side of the bonding film 13 picked up together with the semiconductor element 2 in the pickup process is arranged at the bonding position of the substrate 40 such as a lead frame or a package substrate. Then, the bonding film 13 is heat-treated at a temperature of 250 to 350 ° C. At this time, the tack layer 13b is thermally decomposed, the organic dispersion medium (D) in the conductive bonding layer 13a is removed, and the metal fine particles (M) are melted and diffused to react with the electrodes of the semiconductor element to form an alloyed phase or Form a metal compound phase.
  • the substrate 40 such as a lead frame or a package substrate.
  • the metal fine particles (P) aggregate at a temperature lower than the melting point of the metal in the bulk state due to the energy of the surface, and the bonding (sintering) between the surfaces of the metal fine particles proceeds, and the conductive connecting member made of the metal porous body is formed. 50 is formed.
  • the organic solvent (SC) is contained in the organic solvent (S) during the heat treatment, the solvent exerts a reducing function in the liquid and gaseous states, so that the oxidation of the metal fine particles (P) is suppressed. Sintering is promoted.
  • a drying step is provided in advance prior to the heat treatment to provide the organic solvent (S). ) Can be evaporated and removed.
  • the joining step may be performed without pressurization or may be pressurized. When pressurized, the adhesion between the conductive paste and the lead frame, package substrate, etc. is improved.
  • the conductive connecting member 50 is a porous metal body formed by surface contact between metal fine particles (P) and bonding (sintering), the conductive connecting member 50 has appropriate elasticity and softness, and is conductive. Is not impaired.
  • the porosity of the porous metal body is in the range of 1 to 9% by volume, preferably 1 to 6% by volume, and the average pore diameter is in the range of 10 to 120 nm, preferably 10 to 60 nm.
  • the method for measuring the porosity, the average primary particle size of the metal fine particles, and the average pore diameter in the conductive connecting member 50 is as follows.
  • a wire bonding step is performed in which the tip of the terminal portion (not shown) of the substrate 40 and the electrode pad (not shown) on the semiconductor element 2 are electrically connected by a bonding wire 60.
  • the bonding wire 60 for example, a gold wire, an aluminum wire, a copper wire, or the like is used.
  • the temperature at which wire bonding is performed is preferably 80 ° C. or higher, more preferably 120 ° C. or higher, and the temperature is preferably 250 ° C. or lower, more preferably 175 ° C. or lower.
  • the heating time is several seconds to several minutes (for example, 1 second to 1 minute).
  • the connection is performed by a combination of vibration energy by ultrasonic waves and crimping energy by applied pressurization in a state of being heated so as to be within the temperature range.
  • a sealing step of sealing the semiconductor element 2 with the sealing resin 70 is performed.
  • This step is performed to protect the semiconductor element 2 and the bonding wire 60 mounted on the substrate 40.
  • This step is performed by molding a sealing resin with a mold.
  • the sealing resin 70 for example, an epoxy resin is used.
  • the heating temperature at the time of resin sealing is preferably 165 ° C. or higher, more preferably 170 ° C. or higher, and the heating temperature is preferably 185 ° C. or lower, more preferably 180 ° C. or lower.
  • the sealed material may be further heated (post-curing step).
  • the insufficiently cured sealing resin 70 can be completely cured in the sealing step.
  • the heating temperature can be set as appropriate. As a result, the semiconductor device 100 is manufactured.
  • the bonding film is used when the back surface of the semiconductor element 2 on which the circuit is not formed is bonded to the substrate 40, but the present invention is not limited to this, and the circuit of the semiconductor element 2 is formed. It may be used when joining the surface to which the surface is formed and the substrate 40 (so-called flip chip mounting).
  • Conductive Bonding Layer A 70% by mass of copper fine particles (corresponding to metal fine particles (P)) having an average primary particle size of 150 nm prepared by electroless reduction from copper ions in an aqueous solution, 40% by mass of glycerol as an organic solvent, and N-methylacetamide. 95% by mass of a mixed solvent (corresponding to the organic solvent (S1)) consisting of 55% by mass and 5% by mass of triethylamine, and 30% by mass of an organic dispersion medium consisting of 5% by mass of ethyl cellulose (average molecular weight 1,000,000) as an organic binder.
  • a mixed solvent corresponding to the organic solvent (S1)
  • an organic dispersion medium consisting of 5% by mass of ethyl cellulose (average molecular weight 1,000,000) as an organic binder.
  • a release film (50 ⁇ m polyethylene terephthalate film) is placed on the mounting table, and a SUS spacer that is 350 ⁇ m thick and has a 6 inch circular opening in the center is placed on the release film, and the release film faces from the spacer opening.
  • 5.0 g of the above-mentioned conductive paste was placed on the film, screen printing was performed using a squeegee, and the conductive paste was rolled into a circular sheet shape. Then, after removing the spacer, it was pre-dried for 5 minutes in an inert atmosphere to prepare a conductive bonding layer A.
  • the conductive bonding layer B was formed in the same manner as the conductive bonding layer A except that 70% by mass of silver particles (manufactured by Sigma-Aldrich Japan LLC, model number: 730777) having an average primary particle size of 100 nm were used instead of the copper fine particles. Made.
  • Tack layer composition A Preparation of tack layer
  • 90% by mass of methanol is mixed with 10% by mass of polyglycerin to dilute polyglycerin, and tin fine particles (manufactured by Mitsui Metal Mining Co., Ltd.) having an average primary particle size of 1.5 ⁇ m as metal fine particles (M) are diluted with polyglycerin.
  • a tack layer composition was prepared by dispersing the liquid in an amount of 0.1% by mass by weight using an ultrasonic disperser. The ratio of the metal fine particles (M) to the metal fine particles (P) was 0.1% by weight.
  • Tack layer composition B The tack layer B was prepared in the same manner as the tack layer A except that the tin fine particles were adjusted to 0.5% by weight in weight% with respect to the diluted solution of polyglycerin. The ratio of the metal fine particles (M) to the metal fine particles (P) was 0.5% by weight.
  • Tack layer composition C The tack layer C was prepared in the same manner as the tack layer A except that the tin fine particles were adjusted to 1% by weight in% by weight with respect to the diluted solution of polyglycerin. The ratio of the metal fine particles (M) to the metal fine particles (P) was 1% by weight.
  • the tack layer D was prepared in the same manner as the tack layer A except that the tin nickel-copper alloy fine particles (manufactured by Mitsui Mining & Smelting Co., Ltd.) having an average primary particle size of 1.75 ⁇ m were used instead of the tin fine particles.
  • the ratio of the metal fine particles (M) to the metal fine particles (P) was 0.1% by weight.
  • Tack layer composition E The tack layer E was prepared in the same manner as the tack layer D except that the tin-nickel-copper alloy fine particles were adjusted to 1% by weight in weight% with respect to the polyglycerin diluent. The ratio of the metal fine particles (M) to the metal fine particles (P) was 1% by weight.
  • Tack layer composition F Same as Tuck Layer A except that bismuth alloy fine particles (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) having an average primary particle size of 2.0 ⁇ m were adjusted to 0.5% by weight based on the diluted solution of polyglycerin.
  • the tack layer F was prepared.
  • the ratio of the metal fine particles (M) to the metal fine particles (P) was 0.5% by mass.
  • Tack layer composition G The tack layer G was prepared in the same manner as the tack layer A except that the tin fine particles were adjusted to 0.01% by weight in% by weight with respect to the diluted solution of polyglycerin. The ratio of the metal fine particles (M) to the metal fine particles (P) was 0.01% by weight.
  • Tack layer composition H The tack layer H was prepared in the same manner as the tack layer A except that the tin fine particles were adjusted to 2% by weight in% by weight with respect to the diluted solution of polyglycerin. The ratio of the metal fine particles (M) to the metal fine particles (P) was 2% by weight.
  • Tack Layer Composition I The tack layer I was prepared in the same manner as the tack layer A except that it did not contain metal fine particles.
  • Example 1 Then, on a hot plate warmed to 50 ° C., the above-mentioned tack layer composition A is applied onto the conductive bonding layer A by a spray coating method so that the film thickness after drying is 2 ⁇ m, and the temperature is 50 ° C. for 180 seconds. It was dried to form a tack layer. In this way, the bonding film according to Example 1 was obtained.
  • Examples 2 to 6 Comparative Examples 1 to 5
  • the bonding films according to Examples 2 to 6 and Comparative Examples 1 to 5 were obtained by combining the conductive bonding layer and the tack layer shown in Tables 1 and 2.
  • an adhesive film was produced as follows.
  • a curing agent was added to an acrylic copolymer having a weight average molecular weight of 800,000, which was synthesized by radically polymerizing 65 parts by weight of butyl acrylate, 25 parts by weight of 2-hydroxyethyl acrylate, and 10 parts by weight of acrylic acid and subjecting 2-isocyanate ethyl methacrylate to a drop reaction.
  • 3 parts by weight of polyisocyanate and 1 part by weight of 1-hydroxy-cyclohexyl-phenyl-ketone as a photopolymerization initiator were added and mixed to prepare a pressure-sensitive adhesive layer composition.
  • PP polypropylene
  • Novatec FG4 manufactured by Japan Polychem Corporation was used, and for hydrogenated styrene-butadiene (HSBR), Dynaron 1320P manufactured by JSR Corporation was used.
  • HSBR hydrogenated styrene-butadiene
  • Dynaron 1320P manufactured by JSR Corporation was used.
  • a PET film Teijin: Hupylex S-314, thickness 25 ⁇ m
  • the conductive bonding layer of the bonding film was bonded onto the adhesive layer of the adhesive film to obtain a wafer processing tape.
  • a wafer having various chip electrode layers of Ti / Au, Ti / Ag, Ti / Cu, and Ti / Ni formed on the surface of a semiconductor wafer having a thickness of 230 ⁇ m was prepared.
  • the thickness of each chip was 100 nm.
  • an oxygen-free copper plate having a thickness of 1.2 mm and having a semi-hard temper was prepared.
  • the bonding films according to the above Examples and Comparative Examples were placed on a hot plate heated to 50 ° C. and heated to enhance the tackiness of the tack layer, and the types shown in Tables 1 and 2 were applied to the tack layer.
  • the surface of the semiconductor wafer of the electrode (the surface on the side of the semiconductor element electrode layer) is attached, and then the temperature is returned to room temperature, and the tack layer is cooled and cured using a dicing device (manufactured by DISCO, DAD340 (trade name)). Dicing was performed on a 7 mm ⁇ 7 mm semiconductor chip together with the bonding film. Then, using an ultraviolet irradiator of a high-pressure mercury lamp, ultraviolet irradiation was performed from the base film surface side of the adhesive film so that the irradiation amount was 200 mJ / cm2.
  • the adhesive film is expanded using a die bonder (CPS-6820 (trade name) manufactured by Canon Machinery Inc.), the semiconductor chip is picked up together with the bonding film in that state, and the conductive bonding layer side of the bonding film is used as a substrate. Placed on top.
  • CPS-6820 trade name manufactured by Canon Machinery Inc.
  • the above-mentioned laminate of the semiconductor chip, the bonding film, and the substrate was formed at 300 ° C. for 60 minutes when the conductive bonding layer was formed of the copper fine particle paste, and 250 ° C. for 60 minutes when the conductive bonding layer was formed of the silver fine particle paste. , Each of which was heated to sinter the conductive bonding layer to prepare 20 mounting samples.
  • TCT temperature cycle test
  • the number of TCTs until the failure of the mounting sample using the bonding film according to this example and the comparative example was 2500 to 3000 times was judged as a good product by A, and it was 1000 to 2000 times.
  • a product was judged as a non-defective product by B, and a product that was 1000 times or less was judged as a defective product by Cde.
  • the bonding film including the A judgment in the bonding with all types of electrodes and having a B judgment or higher is evaluated as a good product with ⁇ , and the one having a B judgment in the bonding with all types of electrodes is regarded as a good product. It was evaluated with ⁇ , and those having a C judgment in joining with any of the electrodes were evaluated as defective products with ⁇ .
  • Tables 1 and 2 The results are shown in Tables 1 and 2.
  • Comparative Examples 1 and 2 since the tack layer does not contain metal fine particles (M), the bonding with the substrate may be good depending on the type of the electrode of the semiconductor element. The result was inferior in the temperature cycle test evaluation.
  • Comparative Example 3 since the melting point of the metal fine particles (M) exceeds 250 ° C., an alloy phase with the electrode is not formed, so that the bonding state is not good and the temperature cycle test evaluation is inferior.
  • Comparative Example 4 since the content ratio of the metal fine particles (M) is as small as 0.01% by weight with respect to the metal fine particles (P), the metal fine particles (M) are formed at the interface between the metal porous body and the electrode of the semiconductor element after bonding.
  • the alloy phase between M) and the electrode was not sufficiently formed, and depending on the type of electrode of the semiconductor element, the bonding with the substrate was not good, resulting in poor temperature cycle test evaluation.
  • the metal fine particles (M) are formed at the interface between the metal porous body and the electrode of the semiconductor element after bonding.
  • the alloy phase between the metal and the electrode was formed too thick, and depending on the type of electrode of the semiconductor element, the bonding with the substrate was not good, resulting in poor temperature cycle test evaluation.

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Abstract

接続耐熱性が十分で信頼性が高く、かつ半導体素子の電極の種類によらず、基板との接合が良好で、接合工程が簡易である接合フィルム、ウエハ加工用テープ、接合体の製造方法、接合体および貼合体を提供する。 半導体素子2と基板40とを接合するための接合フィルム13であって、金属微粒子(P)を含む導電性ペーストがフィルム状に成形された導電性接合層13aと、タック性を有し、導電性接合層13aに積層されたタック層13bとを有し、タック層13bは、導電性接合層13a内の金属微粒子(P)に対して、金属微粒子(M)を0.1~1.0質量%含み、前記金属微粒子(M)は融点が250℃以下であることを特徴とする。

Description

接合フィルム、ウエハ加工用テープ、接合体の製造方法、接合体および貼合体
 本発明は、接合フィルムおよびウエハ加工用テープに関し、特に、半導体素子と回路基板やセラミック基板等の基板とを接続するための接続フィルムおよびこれを備えるウエハ加工用テープに関する。
 従来、半導体チップと配線基板等との接着には、フィルム状接着剤(ダイアタッチフィルム)が使用されている。さらに、半導体ウエハを個々のチップに切断分離(ダイシング)する際に半導体ウエハを固定するためのダイシングテープと、切断された半導体チップを配線基板等に接着するためのダイアタッチフィルム(ダイボンディングフィルムともいう)との2つの機能を併せ持つダイシング・ダイボンディングテープが開発されている(例えば、特許文献1参照)。
 このようなダイシング・ダイボンディングテープを、電力の制御や供給等を行う半導体素子(いわゆるパワー半導体素子)と回路基板、セラミック基板およびリードフレーム等の基板との接続に用いた場合、接続耐熱性が十分ではないという問題があった。
 そこで、パワー半導体素子と基板との接続では、一般に半田が使用されている。このような半田としては、半田の粉末にフラックスを加えて適当な粘度にしたクリーム半田が主に用いられている。しかしながら、フラックスを用いると、半導体素子表面を汚染する可能性があり、洗浄工程が必要という問題があった。また、近年、環境上の配慮から、鉛を含まない鉛フリー半田材料を用いることが要求されている。パワー半導体の発熱に対応可能な鉛フリー半田材料としてAu-Sn系半田があるが、高価であるため、実用的ではない。Au-Sn系半田より安価な半田材料としてSn-Ag-Cu系半田があるが、熱履歴による金属間化合物の成長が信頼性の低下につながるという問題があった。
 半田を用いない接合部材として、熱硬化性樹脂に導電性を持つ微細な金属粒子を混ぜ合わせたものを膜状に成形した異方性導電フィルム(Anisotropic Conductive Film:ACF)がある。しかしながら、ACFは、良好な接着状態を得るため、一定割合以上の樹脂を含むため、金属粒子間の接触が点接触となり、十分な熱伝導が期待できず、接続耐熱性が十分ではないという問題点があった。また、ACFは、高熱による熱硬化性樹脂の劣化が懸念されるため、発熱量の大きいパワー半導体の接続には適さない。
 また、他の半田を用いない接合部材として、近時では金属微粒子を含むペースト(以下、金属ペーストという)がある(例えば、特許文献2参照)。 金属ペーストは、金属微粒子に、保存時や製造工程中の金属微粒子同士の凝縮を防止する有機分散剤と、接合時に有機分散剤と反応して有機分散剤を除去する分散補助物質とを添加し、これに溶剤等を混合させてペースト状にしたものである。金属微粒子は、少なくとも粒径が1~500nm程度の極めて微細な粒子を含むものであり、表面は活性状態である。
 金属ペーストを用いて半導体素子と基板とを接合するには、半導体素子および/または基板の接合面に金属ペーストをディスペンサー、またはスクリーン印刷により塗布し、150~300℃で所定時間(1分~1時間程度)加熱する。これにより、有機分散剤と分散補助材とが反応して有機分散剤が除去され、同時に溶剤も揮発して除去される。有機分散剤や溶剤が除去されると、活性状態にある金属微粒子同士が互いに結合し、その金属成分の単体膜となる。
 金属ペーストをディスペンサーやスクリーン印刷を用いて、接合面に塗布する場合、溶剤等の量を調節して、金属ペーストの粘度をある程度低くする必要がある。しかしながら、粘度を下げると、金属ペーストを接合面に塗布する際に、金属ペーストが飛散して半導体素子や基板の接合面以外の部分に付着して半導体素子や基板が汚染されてしまうという問題があった。
 そこで、金属ペーストを予めシート状にした接続シートが提案されている(特許文献3、参照)。しかしながら、特許文献3に記載のような金属ペーストを予めシート状にした接合層を有する接続シートを用いて半導体素子と基板とを接合させる場合、接合層自体には粘着性がないため、吸着治具等を用いて接合層を基板上に載置し、その上に半導体素子を載置して、接合層を焼結させる必要がある。このため、工程が煩雑になるという問題があった。
 上記課題を解決するため、接合層の粘着性問題を改善し、接合工程を簡略化にしたウエハ加工テープが提案されている(特許文献4、参照)。特許文献4に記載の半導体素子と基板とを接合するためのウエハ加工テープは、基材フィルムと該基材フィルム上に設けられた粘着剤層とを有する粘着フィルムと、該粘着フィルム上に設けられ、金属微粒子(P)を含む導電性ペーストがフィルム状に成形された導電性接合層と、タック性を有し、該導電性接合層に積層されたタック層とを有することを特徴としている。
特開2010-265453号公報 特開2006-352080号公報 特開2013-236090号公報 国際公開第2018/092671号
 しかしながら、上記特許文献4に記載のウエハ加工テープでは、導電性接合層を構成した金属微粒子の種類によって接合が可能な半導体素子の種類が限定されるという問題があった。例えば、金属微粒子として銅微粒子を使用した場合は、銅電極または金電極への接合、金属微粒子として銀微粒子を使用した場合は、銀電極または金電極への接合が良好と考えられる、導電性接合層と半導体素子の電極の種類が限定される。
 そこで、本発明は、接続耐熱性が十分で信頼性が高く、かつ半導体素子の電極の種類によらず、基板との接合が良好で、接合工程が簡易である接合フィルム、ウエハ加工用テープ、接合体の製造方法、接合体および貼合体を提供することを目的とする。
 以上の課題を解決するため、本発明に係る接合フィルムは、半導体素子と基板とを接合するための接合フィルムであって、金属微粒子(P)を含む導電性ペーストがフィルム状に成形された導電性接合層と、タック性を有し、前記導電性接合層に積層されたタック層とを有し、前記タック層は、前記導電性接合層内の前記金属微粒子(P)に対して、金属微粒子(M)を0.1~1.0質量%含み、前記金属微粒子(M)は融点が250℃以下であることを特徴とする。
 上記接合フィルムは、前記金属微粒子(P)の平均一次粒径が10~500nmであることが好ましい。
 また、上記接合フィルムは、前記導電性ペーストが有機溶剤(S)を含むことが好ましい。
 また、上記接合フィルムは、前記金属微粒子(P)が銅または銀を含むことが好ましい。
 また、上記接合フィルムは、前記導電性ペーストが有機バインダー(R)を含むことが好ましい。
 また、上記接合フィルムは、前記タック層が、ポリグリセリン、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ホスフィン類、ホスファイト類、スルフィド類、ジスルフィド類、トリスルフィド類、およびスルホキシド類の中から選択される1種もしくは2種以上からなることが好ましい。
 また、上記接合フィルムは、前記金属微粒子(M)も平均一次粒径が1~3μmであることが好ましい。
 また、上記接合フィルムは、前記金属微粒子(M)が錫を含むことが好ましい。
 また、上記接合フィルムは、前記有機溶剤(S)が、常圧における沸点が100℃以上でかつ分子中に1または2以上のヒドロキシル基を有するアルコールおよび/もしくは多価アルコールからなる有機溶剤(SC)を含むことが好ましい。
 また、上記接合フィルムは、前記有機バインダー(R)が、セルロース樹脂系バインダー、アセテート樹脂系バインダー、アクリル樹脂系バインダー、ウレタン樹脂系バインダー、ポリビニルピロリドン樹脂系バインダー、ポリアミド樹脂系バインダー、ブチラール樹脂系バインダー、およびテルペン系バインダーの中から選択される1種または2種以上であることが好ましい。
 また、以上の課題を解決するため、本発明に係るウエハ加工用テープは、基材フィルムと該基材フィルム上に設けられた粘着剤層とを有する粘着フィルムと、上記のいずれかに記載の接合フィルムとを有し、前記粘着剤層上に、前記接合フィルムの導電性接合層が設けられていることを特徴とする。
 また、以上の課題を解決するため、本発明に係る接合体の製造方法は、金属微粒子(P)を含む導電性ペーストがフィルム状に成形された導電性接合層と、タック性を有し金属微粒子(M)を含んで、前記導電性接合層に積層されたタック層とを有する接合フィルムを、半導体素子と基板と間に配置して加熱し、前記タック層が熱分解され、前記金属微粒子(M)が溶融して前記半導体素子の電極と反応した後に、前記導電性接合層の前記金属微粒子(P)を焼結させることによって、前記半導体素子と前記基板とを接合する接合工程を有することを特徴とする。
 また、以上の課題を解決するため、本発明に係る半導体と基板の接合体は、基板上に、金属多孔質体からなる導電接続部材を有し、その上に半導体素子を有する半導体と基板の接合体であって、上記のいずれかに記載の接合フィルムを用いて接合されており、前記金属多孔質体は、上記接合フィルムに含まれる金属微粒子(P)の焼結体であり、前記金属多孔質体と前記半導体素子の電極との界面には、上記接合フィルムに含まれる金属微粒子(M)と前記電極との合金相または金属化合物相が形成されていることを特徴とする。
 上記半導体と基板の接合体は、前記金属多孔質体の空隙率が1~6体積%であり、平均空孔径が10~60nmであることが好ましい。
 また、以上の課題を解決するため、本発明に係る貼合体は、基材フィルムと該基材フィルム上に設けられた粘着剤層とを有する粘着フィルムと、半導体素子と基板とを接合するための接合フィルムと、半導体ウエハとが貼合された貼合体であって、前記接合フィルムは、金属微粒子(P)を含む導電性ペーストがフィルム状に成形された導電性接合層と、タック性を有し、前記導電性接合層に積層されたタック層とを有し、前記導電性接合層が前記粘着剤層に貼合され、前記半導体ウエハは前記タック層に貼合されており、前記タック層は熱分解可能であり、かつ前記導電性接合層内の前記金属微粒子(P)に対して金属微粒子(M)を0.1~1.0重量%含み、接合時の加熱により、前記タック層が熱分解され、金属微粒子(M)が溶融して前記半導体素子の電極と反応した後に、前記導電性接合層の前記金属微粒子(P)が焼結することによって、前記半導体素子と前記基板とが接合されることを特徴とする。
 本発明によれば、接続耐熱性が十分で信頼性が高く、かつ半導体素子の電極の種類によらず、基板との接合が良好で、接合工程が簡易である接合フィルム、ウエハ加工用テープ、接合体の製造方法、接合体および貼合体を提供することができる。
本発明の実施形態に係るウエハ加工用テープを模式的に示す断面図である。 ウエハ加工用テープ上に半導体ウエハを貼り合せた図である。 ダイシング工程を説明するための図である。 エキスパンド工程を説明するための図である。 ピックアップ工程を説明するための図である。 本発明の実施形態に係るウエハ加工用テープを用いて製造された半導体装置を模式的に示す断面図である。
 以下、本発明の実施の形態に係る接着フィルムおよびウエハ加工用テープを図面に基づいて説明する。本発明の一実施形態に係るウエハ加工用テープを図1乃至図5に基づいて説明する。図1は一実施形態に係るウエハ加工用テープ10を示す断面図である。図2は、ウエハ加工用テープ10上に半導体ウエハ1を貼り合せた状態を示す図である。また、図3は、半導体装置の製造工程におけるダイシング工程を説明するための図であり、図4は、エキスパンド工程を説明するための図であり、図5は、ピックアップ工程を説明するための図である。図6は、本発明の実施形態に係るウエハ加工用テープを用いて製造された半導体装置を模式的に示す断面図である。
 図1に示すように、本発明の一実施形態に係るウエハ加工用テープ10は、基材フィルム12aとその上に形成された粘着剤層12bとからなる粘着フィルム12と、この粘着フィルム12上に積層された接合フィルム13とを有する。接合フィルム13は、金属微粒子(P)を含む導電性ペーストがフィルム状に成形された導電性接合層13aと、タック性を有し導電性接合層13aに積層されたタック層13bとを有し、粘着剤層12b上に導電性接合層13aが設けられている。ウエハ加工用テープ10は、半導体ウエハ1を半導体素子2(チップまたは半導体チップともいう)に切断するダイシング工程と、切断された半導体素子2を回路基板、セラミック基板およびリードフレーム等の基板40(図6参照)に接合するダイボンディング工程との両工程に使用される。ダイシング工程については図3を参照して後述する。
 なお、粘着剤層12bは一層の粘着剤層により構成されていても良いし、二層以上の粘着剤層が積層されたもので構成されていても良い。なお、図1においては、接合フィルム13を保護するため、離型フィルム11がウエハ加工用テープ10に設けられている様子が示されている。離型フィルム11としては、公知のものを使用することができる。
 粘着フィルム12および接合フィルム13は、使用工程や装置にあわせて予め所定形状に形成されていても良い。
 以下、本実施形態のウエハ加工用テープ10の各構成要素について詳細に説明する。
 (接合フィルム)
 接合フィルム13は、半導体ウエハ1が貼り合わされてダイシングされた後、個片化された半導体素子2をピックアップする際に、粘着フィルム12から剥離して半導体素子2に付着してピックアップされ、半導体素子2を基板40に固定する際の接合材として使用されるものである。従って、接合フィルム13は、ピックアップ工程において、個片化された半導体素子2に付着したままの状態で、粘着フィルム12から剥離することができる粘着性と剥離性を有し、さらに、半導体素子2と基板40とを接合して、十分な接合信頼性を有するものである。ピックアップ工程については図5を参照して後述する。
 接合フィルム13は、金属微粒子(P)を含む導電性ペーストがフィルム状に成形された導電性接合層13aと、タック性を有し導電性接合層13aに積層されたタック層13bとを有する。
 なお、本発明においてタック性とは、接着性を意味し、具体的には、導電性接合層13aを半導体ウエハ1や半導体素子2に保持させることのできる接着性を意味する。
 [導電性接合層]
 導電性ペーストは、金属微粒子(P)を含む他、有機分散媒(D)を含むことが好ましい。
 導電性ペーストに含まれる金属微粒子(P)(「導電性接合層内金属微粒子」ともいう)としては、銅、マグネシウム、アルミニウム、亜鉛、ガリウム、チタン、マンガン、ゲルマニウム、銀、金、ニッケル、白金およびパラジウムからなる金属元素群から選ばれる1種の微粒子、前記金属元素群から選ばれる2種以上を混合した微粒子、前記金属元素群から選ばれる2種以上の元素の合金からなる微粒子、前記金属元素群から選ばれる1種の微粒子または前記金属元素群から選ばれる2種以上を混合した微粒子と前記金属元素群から選ばれる2種以上の元素の合金からなる微粒子とを混合した微粒子、これらの酸化物、または、これらの水酸化物等を用いることができる。
 金属微粒子(P)は、導電性、加熱処理の際の焼結性を考慮すると、(i)銅微粒子(P1)、または(ii)銅微粒子(P1)90~100質量%と、マグネシウム、アルミニウム、亜鉛、ガリウム、チタン、マンガン、およびゲルマニウムから選択された1種もしくは2種以上の第二の金属微粒子(P2)10~0質量%、からなる金属微粒子を使用することが好ましい。前記銅微粒子(P1)は相対的に導電性の高い金属であり、一方、金属微粒子(P2)は相対的に融点が低い金属である。銅微粒子(P1)に第二の金属微粒子(P2)を併用する場合には、金属微粒子(P2)が金属微粒子(P)中で銅微粒子(P1)と合金を形成しているか、または前記金属微粒子(P2)が金属微粒子(P)中で銅微粒子(P1)の表面で被覆層を形成していることが好ましい。前記銅微粒子(P1)および金属微粒子(P2)を併用することにより、加熱処理温度を低下でき、又金属微粒子間の結合をより容易にすることができる。
 金属微粒子(P)は、加熱処理前の平均一次粒径が10~500nmであることが好ましく、30~300nmであることがより好ましく、100~150nmであることが更に好ましい。金属微粒子(P)の平均一次粒径が10nm未満では、加熱処理(焼結)により焼結体全体に渡って均質な粒径と空孔を形成することが困難になるおそれがあり、熱サイクル特性が低下し、ひいては接合強度も低下する場合がある。一方、該平均一次粒径が500nmを超えると焼結体を構成している金属微粒子および空孔径がミクロンサイズ近くになり、やはり熱サイクル特性が低下する。加熱処理前の金属微粒子(P)の平均一次粒径は、走査型電子顕微鏡(SEM)によりその直径を測定することができる。例えば、二次元形状が略円形状である場合はその円の直径、略楕円形状である場合はその楕円の短径、略正方形状である場合はその正方形の辺の長さ、略長方形状である場合はその長方形の短辺の長さを測定する。「平均一次粒径」は、無作為に10~20個選択された複数の粒子の粒径を上記顕微鏡で観察して計測し、その平均値を計算することによって求められる。
 前記金属微粒子(P)の製造方法としては、特に制限はなく、例えば湿式化学還元法、アトマイズ法、めっき法、プラズマCVD法、MOCVD法等の方法を用いることができる。
 平均一次粒径10~500nmの金属微粒子(P)の製造方法は、具体的には特開2008-231564号公報に開示された方法を採用することができる。該公報に開示された製造方法を採用すると、平均一次粒径が10~500nmの金属微粒子(P)を容易に得ることが可能であり、また該公報に開示された金属微粒子の製造方法において、金属イオンの還元反応終了後に還元反応水溶液に凝集剤を添加して遠心分離等により回収される、反応液中の不純物が除去された金属微粒子に有機分散媒(D)を添加して混練して、本発明の導電性ペーストを製造することができる。
 導電性ペースト中に金属微粒子(P)を均一に分散させるためには、分散性、加熱処理の際の焼結性等に優れる特定の有機分散媒(D)を選択することが重要である。有機分散媒(D)は、導電性ペースト中で金属微粒子(P)を分散させ、導電性ペーストの粘度を調節して、フィルム形状を維持し、かつ加熱処理の際に液状およびガス状で還元剤としての機能を発揮することができる。有機分散媒(D)は、少なくとも有機溶剤(S)を含み、さらに有機バインダー(R)を含むことが好ましい。
 有機溶剤(S)は、常圧における沸点が100℃以上でかつ分子中に1または2以上のヒドロキシル基を有するアルコールおよび/もしくは多価アルコールからなる有機溶剤(SC)を含むことが好ましい。さらには、有機溶剤(S)は、(i)少なくとも、アミド基を有する有機溶剤(SA)5~90体積%、常圧における沸点が20~100℃である低沸点の有機溶剤(SB)5~45体積%、および常圧における沸点が100℃以上で、かつ分子中に1または2以上のヒドロキシル基を有するアルコールおよび/もしくは多価アルコールからなる有機溶剤(SC)5~90体積%含む有機溶剤(S1)、並びに(ii)少なくとも、アミド基を有する有機溶剤(SA)5~95体積%、および常圧における沸点が100℃以上で、かつ分子中に1または2以上のヒドロキシル基を有するアルコールおよび/もしくは多価アルコールからなる有機溶剤(SC)5~95体積%含む有機溶剤(S2)、の中から選択される1種であることが好ましい。
 上記以外の他の有機溶剤成分を配合する場合には、テトラヒドロフラン、ジグライム、エチレンカルボナート、プロピレンカルボナート、スルホラン、ジメチルスルホキシド等の極性有機溶剤を使用することができる。
 有機溶剤(S1)は、少なくとも、アミド基を有する有機溶剤(SA)5~90体積%、常圧における沸点が20~100℃である低沸点の有機溶剤(SB)5~45体積%、並びに常圧における沸点が100℃以上で、かつ分子中に1または2以上のヒドロキシル基を有するアルコールおよび/もしくは多価アルコールからなる有機溶剤(SC)5~90体積%含む有機溶剤である。有機溶剤(SA)は、有機溶剤(S1)中に5~90体積%含まれ、導電性ペースト中で分散性と保存安定性を向上し、更に前記接合面上の導電性接合層を加熱処理して焼結体を形成する際に接合面での密着性を向上する作用を有している。有機溶剤(SB)は、有機溶剤(S1)中に5~45体積%以上含まれ、導電性ペースト中で溶媒分子間の相互作用を低下させ、分散している金属微粒子(P)の有機溶剤(S1)に対する親和性を向上する作用を有している。有機溶剤(SC)は、有機溶剤(S1)中に5~90体積%以上含まれ、導電性ペースト中で分散性と、分散性の一層の長期安定化を図ることが可能になる。また有機溶剤(SC)を混合有機溶剤中に存在させると、その導電性接合層を接合面に配置して加熱処理すると焼結体の均一性が向上し、また有機溶剤(SC)の有する酸化被膜の還元促進効果も働き、導電性の高い接合部材を得ることが出来る。「有機溶剤(S1)は、少なくとも、有機溶剤(SA)5~90体積%、有機溶剤(SB)5~45体積%、並びに有機溶剤(SC)5~90体積%含む有機溶剤である。」とは、有機溶剤(S1)が有機溶剤(SA)、有機溶剤(SB)、および有機溶剤(SC)から前記配合割合で100体積%となるように配合されていてもよく、また前記配合割合の範囲内で、更に本発明の効果を損なわない範囲で他の有機溶剤成分を配合してもよいことを意味するが、この場合、有機溶剤(SA)、有機溶剤(SB)、および有機溶剤(SC)からなる成分が90体積%以上含まれていることが好ましく、95体積%以上がより好ましい。前記配合割合は、有機溶剤(SA)5~70体積%、有機溶剤(SB)5~30体積%、並びに有機溶剤(SC)10~90体積%が好ましい。
 有機溶剤(S2)は、少なくとも、アミド基を有する有機溶剤(SA)5~95体積%、および常圧における沸点が100℃以上で、かつ分子中に1または2以上のヒドロキシル基を有するアルコールおよび/もしくは多価アルコールからなる有機溶剤(SC)5~95体積%含む有機溶剤である。有機溶剤(SA)は、有機溶剤(S2)中に5~95体積%含まれ、該混合有機溶剤中で分散性と保存安定性を向上し、更に導電性ペーストを加熱処理して金属多孔質体を形成する際に接合面での密着性を向上する作用を有している。有機溶剤(SC)は、有機溶剤(S2)中に5~95体積%含まれ、導電性ペースト中で分散性を一層向上させる。また有機溶剤(SA)と有機溶剤(SC)とを有機溶剤(S2)中に存在させると、導電性接合層を接合面上に配置後、加熱処理する際に、比較的低い加熱処理温度でも焼結を進行させることができる。「有機溶剤(S2)は、少なくとも、有機溶剤(SA)5~95体積%、および有機溶剤(SC)5~95体積%含む有機溶剤である。」とは、有機溶剤(S2)が有機溶剤(SA)、および有機溶剤(SC)から前記配合割合で100体積%となるように配合されていてもよく、また前記配合割合の範囲内で更に、本発明の効果を損なわない範囲で他の有機溶剤成分を配合してもよいことを意味するが、この場合、有機溶剤(SA)、および有機溶剤(SC)からなる成分が90体積%以上含まれることが好ましく、95体積%以上がより好ましい。前記配合割合は、有機溶剤(SA)5~80体積%、および有機溶剤(SC)10~90体積%が好ましい。
 以下に上記した有機溶剤(SC)、有機溶剤(SA)、および有機溶剤(SB)の具体例を示す。
 有機溶剤(SC)は、常圧における沸点が100℃以上で、分子中に1または2以上のヒドロキシル基を有するアルコールおよび/または多価アルコールからなり、還元性を有する有機化合物である。また、炭素数が5以上のアルコール、および炭素数が2以上の多価アルコールが好ましく、常温で液状であり、比誘電率が高いもの、例えば10以上のものが好ましい。平均一次粒径10~500nmの金属微粒子(P)は微粒子の表面積が大きいので酸化の影響を考慮する必要があるが、以下に挙げる有機溶剤(SC)は加熱処理(焼結)の際に液状およびガス状で還元剤としての機能を発揮するので、加熱処理の際に金属微粒子(P)の酸化を抑制して焼結を促進する。有機溶剤(SC)の具体例として、エチレングリコール、ジエチレングリコール、1,2-プロパンジオール、1,3-プロパンジオール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、2-ブテン-1,4-ジオール、2,3-ブタンジオール、ペンタンジオール、ヘキサンジオール、オクタンジオール、グリセロール、1,1,1-トリスヒドロキシメチルエタン、2-エチル-2-ヒドロキシメチル-1,3-プロパンジオール、1,2,6-ヘキサントリオール、1,2,3-ヘキサントリオール、1,2,4-ブタントリオール等が例示できる。
 また、有機溶剤(SC)の具体例として、トレイトール(D-Threitol)、エリトリトール(Erythritol)、ペンタエリスリトール(Pentaerythritol)、ペンチトール(Pentitol)、ヘキシトール(Hexitol)等の糖アルコール類も使用可能であり、ペンチトールには、キシリトール(Xylitol)、リビトール(Ribitol)、アラビトール(Arabitol)が含まれる。前記ヘキシトールには、マンニトール(Mannitol)、ソルビトール(Sorbitol)、ズルシトール(Dulcitol)等が含まれる。更に、グリセロールアルデヒド(Glyceric aldehyde)、ジオキシアセトン(Dioxy-acetone)、トレオース(threose)、エリトルロース(Erythrulose)、エリトロース(Erythrose)、アラビノース(Arabinose)、リボース(Ribose)、リブロース(Ribulose)、キシロース(Xylose)、キシルロース(Xylulose)、リキソース(Lyxose)、グルコース(Glucose)、フルクトース(Fructose)、マンノース(Mannose)、イドース(Idose)、ソルボース(Sorbose)、グロース(Gulose)、タロース(Talose)、タガトース(Tagatose)、ガラクトース(Galactose)、アロース(Allose)、アルトロース(Altrose)、ラクト-ス(Lactose)、イソマルトース(Isomaltose)、グルコヘプトース(Gluco-heptose)、ヘプトース(Heptose)、マルトトリオース(Maltotriose)、ラクツロース(Lactulose)、トレハロース(Trehalose)、等の糖類も使用可能であるが融点が高いものについては他の融点の低い有機溶剤(SC)と混合して使用することが可能である。上記アルコール類のなかでは、分子中に2個以上のヒドロキシル基を有する多価アルコールがより好ましく、エチレングリコールおよびグリセロールが特に好ましい。
 有機溶剤(SA)は、アミド基(-CONH-)を有する化合物であり、特に比誘電率が高いものが好ましい。有機溶剤(A)として、N-メチルアセトアミド(191.3 at 32℃)、N-メチルホルムアミド(182.4 at 25℃)、N-メチルプロパンアミド(172.2 at 25℃)、ホルムアミド(111.0 at 20℃)、N,N-ジメチルアセトアミド(37.78 at 25℃)、1,3-ジメチル-2-イミダゾリジノン(37.6 at 25℃)、N,N-ジメチルホルムアミド(36.7 at 25℃)、1-メチル-2-ピロリドン(32.58 at 25℃)、ヘキサメチルホスホリックトリアミド(29.0 at 20℃)、2-ピロリジノン、ε-カプロラクタム、アセトアミド等が挙げられるが、これらを混合して使用することもできる。尚、上記アミド基を有する化合物名の後の括弧中の数字は各溶媒の測定温度における比誘電率を示す。これらの中でも測定温度20~32℃における比誘電率が100以上である、N-メチルアセトアミド、N-メチルホルムアミド、N-メチルプロパンアミド、ホルムアミドなどが好適に使用できる。尚、測定温度域20~32℃は、ペースト化、フィルム化加工温度に相当し、その際の比誘電率が100以上であることにより、フィルム化前のペースト化工程での金属微粒子(P)の凝集を抑制し、フィルム加工性を向上させるため、重要な温度範囲となる。尚、N-メチルアセトアミド(融点:26~28℃)のように常温で固体の場合には他の溶剤と混合して処理温度で液状として使用することができる。
 有機溶剤(SB)は、常圧における沸点が20~100℃の範囲、好ましくは60.0~100℃の範囲にある有機化合物である。常圧における沸点が20℃未満であると、有機溶剤(SB)を含む粒子分散液を常温で保存した際、有機溶剤(SB)の成分が揮発し、ペースト組成が変化してしまうおそれがある。また常圧における沸点が100℃以下の場合に、該溶媒添加による溶媒分子間の相互引力を低下させ、微粒子の分散性を更に向上させる効果が有効に発揮されることが期待できる。更に、常圧における沸点が60℃以上の場合は、混練の際に冷却しなくても安定的に製造できるため、好ましい。有機溶剤(SB)として、一般式R1-O-R2(R1、R2は、それぞれ独立にアルキル基で、炭素原子数は1~4である。)で表されるエーテル系化合物(SB1)、一般式R3-OH(R3は、アルキル基で、炭素原子数は1~4である。)で表されるアルコール(SB2)、一般式R4-C(=O)-R5(R4、R5は、それぞれ独立にアルキル基で、炭素原子数は1~2である。)で表されるケトン系化合物(SB3)、および一般式R6-(N-R7)-R8(R6、R7、R8は、それぞれ独立にアルキル基、または水素原子で、炭素原子数は0~2である。)で表されるアミン系化合物(SB4)が例示できる。
 以下に上記有機溶剤(SB)を例示するが、化合物名の後のカッコ内の数字は常圧における沸点を示す。前記エーテル系化合物(SB1)としては、ジエチルエーテル(35℃)、メチルプロピルエーテル(31℃)、ジプロピルエーテル(89℃)、ジイソプロピルエーテル(68℃)、メチル-t-ブチルエーテル(55.3℃)、t-アミルメチルエーテル(85℃)、ジビニルエーテル(28.5℃)、エチルビニルエーテル(36℃)、アリルエーテル(94℃)等が例示できる。前記アルコール(SB2)としては、メタノール(64.7℃)、エタノール(78.0℃)、1-プロパノール(97.15℃)、2-プロパノール(82.4℃)、2-ブタノール(100℃)、2-メチル2-プロパノール(83℃)等が例示できる。前記ケトン系化合物(SB3)としては、アセトン(56.5℃)、メチルエチルケトン(79.5℃)、ジエチルケトン(100℃)等が例示できる。また、前記アミン系化合物(SB4)としては、トリエチルアミン(89.7℃)、ジエチルアミン(55.5℃)等が例示できる。
 有機バインダー(R)は、導電性ペースト中で金属微粒子(P)の凝集の抑制、導電性ペーストの粘度の調節、および導電接続部材前駆体の形状を維持する機能を発揮する。前記有機バインダー(R)は、セルロース樹脂系バインダー、アセテート樹脂系バインダー、アクリル樹脂系バインダー、ウレタン樹脂系バインダー、ポリビニルピロリドン樹脂系バインダー、ポリアミド樹脂系バインダー、ブチラール樹脂系バインダー、およびテルペン系バインダーの中から選択される1種または2種以上が好ましい。具体的には、前記セルロース樹脂系バインダーがアセチルセルロース、メチルセルロース、エチルセルロース、ブチルセルロース、およびニトロセルロース;アセテート樹脂系バインダーがメチルグリコールアセテート、エチルグリコールアセテート、ブチルグリコールアセテート、エチルジグリコールアセテート、およびブチルジグリコールアセテート;アクリル樹脂系バインダーがメチルメタクリレート、エチルメタクリレート、およびブチルメタクリレート;ウレタン樹脂系バインダーが2,4-トリレンジイソシアネート、およびp-フェニレンジイソシアネート;ポリビニルピロリドン樹脂系バインダーがポリビニルピロリドン、およびN-ビニルピロリドン;ポリアミド樹脂系バインダーがポリアミド6、ポリアミド66、およびポリアミド11;ブチラール樹脂系バインダーがポリビニルブチラール;テルペン系バインダーがピネン、シネオール、リモネン、およびテルピネオール、の中から選択される1種または2種以上であることが好ましい。
 導電性ペーストは、金属微粒子(P)と、有機溶剤(S)からなる有機分散媒(D)とを含む導電性ペースト、または、前記金属微粒子(P)と、有機溶剤(S)および有機バインダー(R)からなる有機分散媒(D)とを含む導電性ペーストである。これに加熱処理すると、ある温度に達すると有機溶剤(S)の蒸発、または有機溶剤(S)の蒸発と有機バインダー(R)の熱分解が進行して、金属微粒子(P)の表面が現れ、互いに表面で結合(焼結)する原理を利用して接合材として機能するものである。前記導電性ペースト中の、金属微粒子(P)と有機分散媒(D)との配合割合(P/D)は50~85質量%/50~15質量%(質量%の合計は100質量%)であることが好ましい。尚、本発明の効果を損なわない範囲で、本発明の導電性ペーストに上述以外の金属微粒子、有機分散媒等を配合することができる。
 金属微粒子(P)の配合割合が前記85質量%を超えるとペーストが高粘度となり、加熱処理において金属微粒子(P)表面間の結合不足が生じて導電性が低下するおそれがある。一方、金属微粒子(P)の配合割合が前記50質量%未満では、ペーストの粘度が低下してフィルム形状維持が困難となり、また加熱処理の際に収縮という不具合が生ずるおそれがあり、更に、加熱処理する際に有機分散媒(D)の蒸発する速度が遅くなる不都合を伴うおそれもある。かかる観点から、前記金属微粒子(P)と有機分散媒(D)との配合割合(P/D)は55~80質量%/45~20質量%であることがより好ましい。また、該有機分散媒(D)中の有機溶剤(S)と有機バインダー(R)との配合割合(S/R)は80~100質量%/20~0質量%(質量%の合計はいずれも100質量%)であることが好ましく、85~95質量%/15~5質量%であることがより好ましい。
 有機分散媒(D)中の有機バインダー(R)の配合割合が20質量%を超えると、導電性接合層13aを加熱処理する際に有機バインダー(R)が熱分解して飛散する速度が遅くなり、また導電接続部材中に残留カーボン量が増えると焼結が阻害されて、クラック、剥離等の問題が生ずる可能性があり好ましくない。有機溶剤(S)の選択により、該溶剤のみで金属微粒子(P)を均一に分散させ、導電性ペーストの粘度の調節、およびフィルム形状を維持できる機能を発揮できる場合には、有機分散媒(D)として有機溶剤(S)のみからなる成分を使用できる。導電性ペーストには、前記した成分に必要に応じて消泡剤、分散剤、可塑剤、界面活性剤、増粘剤など公知の添加物を加えることができる。導電性ペーストを製造する際に、各成分を混合した後にボールミル等を用いて混練することができる。
 [タック層]
 タック層13bは、導電性接合層13aを半導体ウエハ1や半導体素子2に保持させるためのものであり、タック性を有している。また、タック層13bは、半導体素子2と基板40とを接合する際の加熱により熱分解される。タック層13bは、このような性質を有するものであれば、特に限定されるものではなくどのようなもので構成されていてもよい。
 タック層13bは、導電性接合層13aにはタック性がないため、半導体ウエハ1や半導体素子2と導電性接合層13aとの接着性を改善するための層である。タック層13bがないと、半導体ウエハ1や半導体素子2と導電性接合層13aとの接着力が弱いため、半導体ウエハ1のダイシング時や半導体素子2のピックアップ時に、半導体ウエハ1や半導体素子2と導電性接合層13aとの間で剥離してしまう。また、タック層13bは、導電性接合層13aの半導体ウエハ1や半導体素子2への密着力を上げるための層でもある。密着力が上がることにより、導電性接合層13aを介して半導体素子2と基板40とを接合させたときの接合強度も向上する。
 本発明においては、タック層13bが半導体素子2と基板40とを接合する際の加熱で熱分解されることにより、半導体素子2と基板40とが導電性接合層13aを介して機械的に接合されることが重要である。このため、タック層13bは、接合時の加熱温度で、空気雰囲気下、昇温速度5℃/分の熱重量測定における重量減少が70重量%以上であることが好ましく、さらに好ましくは85重量%以上、さらに好ましくは95重量%以上である。
 また、タック層13bは、接合時に半導体素子2と直接接触しているため、半導体素子2の電極の表面を活性化させる効果も期待される。これは、タック層13bに含まれる物質が加熱時分解する際に、金属である電極表面の酸化層と反応して金属面をクリーニングするためと考えられる。このように半導体素子2の電極の表面が活性化されることにより、半導体素子2の電極と導電性接合層13aとの密着力を向上させることができる。
 タック層13bを構成する材料としては、極性もしくは非極性溶媒中に、室温では溶けないが、融点まで加熱すると溶けやすいものを用いることが好ましい。このような材料を融点まで加熱して溶媒中に溶かし、導電性接合層13a等の上に塗布した後、室温まで冷却し、溶媒を蒸発させることによりタック性を有する膜状体を形成することができる。溶媒としては、公知の溶剤を適宜使用することができるが、成膜時の蒸発を容易にするため低沸点の溶剤を用いることが好ましい。低沸点の溶媒として、有機溶剤(SB)を用いることもできる。
 さらに、タック層13bは、導電性ペースト中の金属微粒子(P)を加熱焼結させる際に、金属微粒子(P)を還元させる物質で構成されることがより好ましい。タック層13bの分解反応が多段反応で起きる物質では反応温度領域が広く、金属微粒子(P)が還元され、これにより金属微粒子(P)の焼結後の抵抗率が下がり、導電性が向上する。
 タック層13bは、例えば、ポリグリセリン(融点:23℃);グリセリンモノカプレート(融点:46℃)、グリセリンモノラウレート(融点:57℃)、グリセリンモノステアレート(融点:70℃)、グリセリンモノベヘネート(融点:85℃)等のグリセリン脂肪酸エステル;ジグリセリンステアレート(融点:61℃)、ジグリセリンラウレート(融点:34℃)等のポリグリセリン脂肪酸エステル;スチレンp-スチリルジフェニルホスフィン(融点:75℃)、トリフェニルホスフィン(融点:81℃)、トリ-n-オクチルホスフィン(融点:30℃)等のホスフィン類;ホスファイト類;ビス(4-メタクリロイルチオフェニル)スルフィド(融点:64℃)、フェニルp-トリルスルフィド(融点:23℃)、フルフリルスルフィド(融点:32℃)等のスルフィド類;ジフェニルジスルフィド(融点:61℃)、ベンジルジスルフィド(融点:72℃)、テトラエチルチウラムジスルフィド(融点:70℃)等のジスルフィド類;トリスルフィド類;およびスルホキシド類の中から選択される1種もしくは2種以上からなることが好ましい。
 また、タック層13bは、タック性および熱分解性を阻害せず、半導体素子2や基板40への汚染や突沸ガス発生の面で問題が生じない範囲で、必要に応じて消泡剤、分散剤、可塑剤、界面活性剤、増粘剤など公知の添加物を加えることができる。
 タック層13bは、導電性接合層13a内の金属微粒子(P)に対して、金属微粒子(M)(「タック層内金属微粒子」ともいう)を0.1~1.0質量%含んでいる。金属微粒子(M)は融点が250℃以下である。金属微粒子(M)は錫またはその合金微粒子であることが好ましく、例えば、Snはんだの粉末、SnNiCu、SnNiCu(Ge)、SnAgCu、またはSnAuの粉末などが使用できる。タック層13bに、金属微粒子(M)を導電性接合層13a内の金属微粒子(P)に対して0.1~1.0質量%添加することにより、接合時の熱でタック層13bが熱分解され、金属微粒子(M)が溶融して半導体素子の電極と拡散反応し合金化相または金属化合物相(以下、拡散層ともいう)を形成するため、導電性接合層13aと半導体素子2の電極との接合性がよくなり、導電性接合層13aを構成する金属微粒子(P)の種類や電極の種類にかかわらず、良好に接合することができる。
 金属微粒子(M)は、平均一次粒径が1~3μmであることが好ましく、形成する拡散相の厚さをより薄くするためには1~2μmであることがより好ましい。金属微粒子(M)の平均一次粒径が1μm未満では、サイズ効果で低温から焼結し始め、焼結初期段階から粒径が大きくなるまたは粒径のバラツキが生じ、電極との拡散反応が悪くなるまたは拡散相のバラツキが出てしまうおそれがある。また、該平均一次粒径が3μmを超えると拡散反応による拡散相が厚くできてしまい、接合体の導電性および放熱性を阻止するおそれがある。金属微粒子(M)の平均一次粒径は、走査型電子顕微鏡(SEM)によりその直径を測定することができる。例えば、二次元形状が略円形状である場合はその円の直径、略楕円形状である場合はその楕円の短径、略正方形状である場合はその正方形の辺の長さ、略長方形状である場合はその長方形の短辺の長さを測定する。「平均一次粒径」は、無作為に10~20個選択された複数の粒子の粒径を上記顕微鏡で観察して計測し、その平均値を計算することによって求められる。
 次に、接合フィルム13を製造する方法について説明する。まず、載置台の上に、離型フィルムを載置し、離型フィルムの上にスペーサーを配置する。スペーサーは、例えばSUS等の金属製の板で、中央部に円形の開口部を有している。スペーサーの開口部であって離型フィルムの上に、上述の導電性ペーストを配置し、スキージを用いてスクリーン印刷を行って導電性ペーストを均一に圧延することにより、導電性ペーストが円形のフィルム状になる。その後、離型フィルムおよびスペーサーを除去する。そして、円形のフィルム状に成形された導電性ペーストを予備乾燥させることにより、導電性接合層13aが形成される。予備乾燥の時間は、印刷厚によるが、例えば5~20分に設定することができる。
 その後、上述のタック層13bの構成成分の材料を加熱して溶剤中で混錬し、導電性接合層13a上にスキージ法あるいはスプレーコート法等を用いて塗布し、冷却する。その後、加熱乾燥させて溶剤を蒸発させることにより、タック層13bが形成される。
 なお、本実施形態においては、本発明の接合フィルム13は、粘着フィルム12上に設けられ、全体としてウエハ加工用テープ10を構成するようにしたが、ウエハ加工用テープ10を製造する材料として接合フィルム13単体で取引されてもよく、その場合、接合フィルム13は、両面を保護フィルムにより保護されていることが好ましい。保護フィルムとしては、ポリエチレン系、ポリスチレン系、ポリエチレンテレフタレート(PET)系、その他、離型処理がされたフィルム等公知のものを使用することができるが、接合フィルム13を保持するのに適した硬さを有するという観点から、ポリエチレンフィルムまたはポリスチレンフィルムを用いることが好ましい。保護フィルムの厚さは、特に限定されるものではなく、適宜に設定してよいが、10~300μmが好ましい。
 (粘着フィルム)
 粘着フィルム12は、半導体ウエハ1をダイシングする際には接合フィルム13に保持された半導体ウエハ1が剥離しないように十分な粘着力を有し、ダイシング後に個片化された半導体素子2をピックアップする際には容易に接合フィルム13から剥離できるような低い粘着力を有するものである。本実施形態において、粘着フィルム12は、図1に示すように、基材フィルム12aに粘着剤層12bを設けたものを例示したが、これに限定されるものではなく、ダイシングテープとして使用される公知の粘着フィルムを用いることができる。
 粘着フィルム12の基材フィルム12aとしては、従来公知のものであれば特に制限することなく使用することができるが、後述するように、本実施形態においては、粘着剤層12bとして、エネルギー硬化性の材料のうち放射線硬化性の材料を使用することから、放射線透過性を有するものを使用する。
 例えば、基材フィルム12aの材料として、ポリエチレン、ポリプロピレン、エチレンプロピレン共重合体、ポリブテン-1、ポリ-4-メチルペンテン-1、エチレン-酢酸ビニル共重合体、エチレン-アクリル酸エチル共重合体、エチレン-アクリル酸メチル共重合体、エチレン-アクリル酸共重合体、アイオノマーなどのα-オレフィンの単独重合体または共重合体あるいはこれらの混合物、ポリウレタン、スチレン-エチレン-ブテン共重合体もしくはペンテン系共重合体、ポリアミド-ポリオール共重合体等の熱可塑性エラストマー、およびこれらの混合物を列挙することができる。また、基材フィルム12aはこれらの群から選ばれる2種以上の材料が混合されたものでもよく、これらが単層または複層化されたものでも良い。基材フィルム12aの厚さは、特に限定されるものではなく、適宜に設定して良いが、50~200μmが好ましい。
 本実施形態においては、紫外線などの放射線を粘着フィルム12に照射することにより、粘着剤層12bを硬化させ、粘着剤層12bを接合フィルム13から剥離しやすくしていることから、粘着剤層12bの樹脂には、粘着剤に使用される公知の塩素化ポリプロピレン樹脂、アクリル樹脂、ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、付加反応型オルガノポリシロキサン系樹脂、シリコンアクリレート樹脂、エチレン-酢酸ビニル共重合体、エチレン-アクリル酸エチル共重合体、エチレン-アクリル酸メチル共重合体、エチレン-アクリル酸共重合体、ポリイソプレンやスチレン・ブタジエン共重合体やその水素添加物等の各種エラストマー等やその混合物に、放射線重合性化合物を適宜配合して粘着剤を調製することが好ましい。また、各種界面活性剤や表面平滑化剤を加えても良い。粘着剤層12bの厚さは、特に限定されるものではなく、適宜に設定して良いが、5~30μmが好ましい。
 放射線重合性化合物としては、例えば、光照射によって三次元網状化しうる分子内に光重合性炭素-炭素二重結合を少なくとも2個以上有する低分子量化合物や、光重合性炭素-炭素二重結合基を置換基に持つポリマーやオリゴマーが用いられる。具体的には、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールモノヒドロキシペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、1,4-ブチレングリコールジアクリレート、1,6ヘキサンジオールジアクリレート、ポリエチレングリコールジアクリレートや、オリゴエステルアクリレート等、シリコンアクリレート等、アクリル酸や各種アクリル酸エステル類の共重合体等が適用可能である。
 また、上記のようなアクリレート系化合物のほかに、ウレタンアクリレート系オリゴマーを用いることもできる。ウレタンアクリレート系オリゴマーは、ポリエステル型またはポリエーテル型などのポリオール化合物と、多価イソシアナート化合物(例えば、2,4-トリレンジイソシアナート、2,6-トリレンジイソシアナート、1,3-キシリレンジイソシアナート、1,4-キシリレンジイソシアナート、ジフェニルメタン4,4-ジイソシアナートなど)を反応させて得られる末端イソシアナートウレタンプレポリマーに、ヒドロキシル基を有するアクリレートあるいはメタクリレート(例えば、2-ヒドロキシエチルアクリレート、2-ヒドロキシエチルメタクリレート、2-ヒドロキシプロピルアクリレート、2-ヒドロキシプロピルメタクリレート、ポリエチレングリコールアクリレート、ポリエチレングリコールメタクリレートなど)を反応させて得られる。なお、粘着剤層12bには、上記の樹脂から選ばれる2種以上が混合されたものでも良い。
 なお、粘着剤層12bの組成物としては、放射線の照射により硬化する放射線重合性化合物の他、アクリル系粘着剤、光重合開始剤、硬化剤等を適宜配合した組成物を用いることもできる。
 光重合開始剤を使用する場合、例えばイソプロピルベンゾインエーテル、イソブチルベンゾインエーテル、ベンゾフェノン、ミヒラーズケトン、クロロチオキサントン、ドデシルチオキサントン、ジメチルチオキサントン、ジエチルチオキサントン、ベンジルジメチルケタール、α-ヒドロキシシクロヘキシルフェニルケトン、2-ヒドロキシメチルフェニルプロパン等を使用することができる。これら光重合開始剤の配合量はアクリル系共重合体100質量部に対して0.01~5質量部が好ましい。
 粘着フィルム12は、ダイシングテープの製造方法として従来公知の方法により製造することができる。ウエハ加工用テープ10は、粘着フィルム12の粘着剤層12b上に、上述の導電性接合層13の導電性接合層13aを貼合することにより、製造することができる。
(ウエハ加工用テープの使用方法)
 半導体装置100(図6参照)の製造工程の中で、ウエハ加工用テープ10は、以下のように使用される。図2においては、ウエハ加工用テープ10に、半導体ウエハ1とリングフレーム20とが貼り合わされた様子が示されている。
 まず、図2に示すように、粘着フィルム12の粘着剤層12bをリングフレーム20に貼り付け、半導体ウエハ1を接合フィルム13のタック層13bに貼り合わせる。これらの貼り付け順序に制限はなく、半導体ウエハ1を接合フィルム13に貼り合わせた後に粘着フィルム12の粘着剤層12bをリングフレーム20に貼り付けても良い。また、粘着フィルム12のリングフレーム20への貼り付けと、半導体ウエハ1の接合フィルム13への貼り合わせとを、同時に行っても良い。
 そして、図3に示すように、半導体ウエハ1のダイシング工程を実施し、次いで、粘着フィルム12にエネルギー線、例えば紫外線を照射する工程を実施する。具体的には、まず、ダイシングブレード21によって半導体ウエハ1と接合フィルム13とをダイシングするため、吸着ステージ22により、ウエハ加工用テープ10を粘着フィルム12面側から吸着支持する。そして、ダイシングブレード21によって半導体ウエハ1と接合フィルム13を半導体素子2単位に切断して個片化し、その後、粘着フィルム12の下面側からエネルギー線を照射する。このエネルギー線照射によって、粘着剤層12bを硬化させてその粘着力を低下させる。なお、エネルギー線の照射に代えて、加熱などの外部刺激によって粘着フィルム12の粘着剤層12bの粘着力を低下させても良い。粘着剤層12bが二層以上の粘着剤層により積層されて構成されている場合、各粘着剤層の内の一層または全層をエネルギー線照射によって硬化させて、各粘着剤層の内の一層または全層の粘着力を低下させても良い。
 その後、図4に示すように、ダイシングされた半導体素子2および接合フィルム13を保持した粘着フィルム12をリングフレーム20の周方向に引き伸ばすエキスパンド工程を実施する。具体的には、ダイシングされた複数の半導体素子2および接合フィルム13を保持した状態の粘着フィルム12に対して、中空円柱形状の突き上げ部材30を、粘着フィルム12の下面側から上昇させ、粘着フィルム12をリングフレーム20の周方向に引き伸ばす。
 エキスパンド工程を実施した後、図5に示すように、粘着フィルム12をエキスパンドした状態のままで、半導体素子2をピックアップするピックアップ工程を実施する。具体的には、粘着フィルム12の下面側から半導体素子2をピン31によって突き上げるとともに、粘着フィルム12の上面側から吸着冶具32で半導体素子2を吸着することで、個片化された半導体素子2を接合フィルム13とともにピックアップする。
 そして、ピックアップ工程を実施した後、接合工程を実施する。具体的には、ピックアップ工程で半導体素子2とともにピックアップされた接合フィルム13の導電性接合層13a側をリードフレームやパッケージ基板等の基板40の接合位置に配置する。その後、接合フィルム13を250~350℃の温度で加熱処理する。このとき、タック層13bが熱分解するとともに、導電性接合層13a中の有機分散媒(D)が除去され、金属微粒子(M)が溶融して半導体素子の電極と拡散反応し合金化相または金属化合物相を形成する。また、金属微粒子(P)が、その表面のエネルギーによってバルク状態の金属の融点より低温で凝集して、金属微粒子表面間での結合(焼結)が進み、金属多孔質体からなる
導電接続部材50が形成される。加熱処理の際に有機溶剤(S)中に、有機溶剤(SC)が含有されていると、該溶剤が液状及び気体状で還元機能を発揮するので、金属微粒子(P)の酸化が抑制されて焼結が促進される。なお、導電性接合層13a中の有機分散媒(D)として比較的低沸点の有機溶剤(S)が含有されている場合には、加熱処理に先立ち、予め乾燥工程を設けて有機溶剤(S)の少なくとも一部を蒸発、除去しておくことができる。このような加熱処理により、半導体素子2と基板40とが機械的に接合される。なお、接合工程は無加圧で行ってもよく、加圧してもよい。加圧された場合、導電性ペーストとリードフレームやパッケージ基板等との密着性が向上される。
 導電接続部材50は、金属微粒子(P)同士が面接触し、結合(焼結)して形成された金属多孔質体であるので、適度な弾力性と柔らかさを有し、かつ、導電性も損なわれることがない。金属多孔質体の空隙率が1~9体積%、好ましくは1~6体積%の範囲で、平均空孔径が10~120nm、好ましくは10~60nmの範囲である。尚、導電接続部材50における、空隙率、金属微粒子の平均一次粒径、及び平均空孔径の測定方法は次の通りである。
(1)金属微粒子の平均一次粒径の測定方法
 金属微粒子を走査型電子顕微鏡(SEM)によって、無作為に10個選択された粒子の断面を観察し、その断面の二次元形状に対する最大内接円の直径を測定し、その平均値を求める。尚、電子顕微鏡の断面写真において、二次元形状が略円形状である場合はその円の直径、略楕円形状である場合はその楕円の短径、略正方形状である場合はその正方形の辺の長さ、略長方形状である場合はその長方形の短辺の長さを測定する。
(2)平均空孔径の測定方法
 「平均空孔径」は、走査型電子顕微鏡(SEM)を用いて無作為に選択された10~20の空孔径の断面形状を観察して計測し、その平均値とする。
(3)空隙率の測定方法
 空隙率の測定は、透過型電子顕微鏡(TEM)により、電子顕微鏡写真を撮り、その断面像の解析で決定することができる。また、空孔サイズが100nmより小さい場合の空隙率はウルトラミクロトーム法により薄片化することで、透過型電子顕微鏡(TEM)で観察して測定する。
 その後、図6に示すように、基板40の端子部(図示しない)の先端と半導体素子2上の電極パッド(図示しない)とをボンディングワイヤー60で電気的に接続するワイヤーボンディング工程を行う。ボンディングワイヤー60としては、例えば金線、アルミニウム線又は銅線などが用いられる。ワイヤーボンディングを行う際の温度は、好ましくは80℃以上、より好ましくは120℃以上であり、該温度は、好ましくは250℃以下、より好ましくは175℃以下である。また、その加熱時間は数秒~数分間(例えば、1秒~1分間)行われる。結線は、前記温度範囲内となる様に加熱された状態で、超音波による振動エネルギーと印加加圧による圧着エネルギーの併用により行われる。
 続いて、封止樹脂70により半導体素子2を封止する封止工程を行う。本工程は、基板40に搭載された半導体素子2やボンディングワイヤー60を保護する為に行われる。本工程は、封止用の樹脂を金型で成型することにより行う。封止樹脂70としては、例えばエポキシ系の樹脂を使用する。樹脂封止の際の加熱温度は、好ましくは165℃以上、より好ましくは170℃以上であり、加熱温度は、好ましくは185℃以下、より好ましくは180℃以下である。
 必要に応じて、封止物を更に加熱をしてもよい(後硬化工程)。これにより、封止工程で硬化不足の封止樹脂70を完全に硬化できる。加熱温度は適宜設定できる。これにより、半導体装置100が製造される。
 なお、上述の例では、接合フィルムを半導体素子2の回路が形成されていない裏面と基板40とを接合する場合に用いたが、これに限定されるものではなく、半導体素子2の回路が形成されている表面と基板40を接合(いわゆるフリップチップ実装)する場合に用いてもよい。
 次に、本発明の実施例について説明するが、本発明はこれら実施例に限定されるものではない。
[導電性接合層の作製]
(導電性接合層A)
 水溶液中で銅イオンからの無電解還元により調製された、平均一次粒径150nmの銅微粒子(金属微粒子(P)に相当する)70質量%と、有機溶剤としてグリセロール40体積%、N-メチルアセトアミド55体積%、及びトリエチルアミン5体積%からなる混合溶剤(有機溶剤(S1)に相当する)95質量%と有機バインダーとしてエチルセルロース(平均分子量1000,000)5質量%からなる有機分散媒30質量%とを混錬して、導電性ペーストを調製した。
 載置台の上に、離型フィルム(50μmのポリエチレンテレフタレートフィルム)、その上に、350μm厚で中央部に6inchの円形の開口を有するSUS製のスペーサーを配置し、スペーサーの開口部から臨む離型フィルムの上に、上述の導電性ペーストを5.0g載置し、スキージを用いてスクリーン印刷を行って導電性ペーストを圧延し、円形のシート形状に成形した。そして、スペーサーを除去した後、不活性雰囲気中で5分間予備乾燥を行い、導電性接合層Aを作製した。
(導電性接合層B)
 銅微粒子に替えて、平均一次粒径100nmの銀微粒子(シグマ アルドリッチ ジャパン合同会社製、型番:730777)70質量%を用いた他は導電性接合層Aと同様にして、導電性接合層Bを作製した。
[タック層の作製]
(タック層組成物A)
 また、ポリグリセリン10質量%にメタノール90質量%を混合させ、ポリグリセリンを希釈し、金属微粒子(M)として平均一次粒径1.5μmの錫微粒子(三井金属鉱業株式会社製)をポリグリセリン希釈液に対して重量%で0.1重量%になるように超音波分散機を用いて分散させ、タック層組成物を調製した。金属微粒子(P)に対する金属微粒子(M)の割合は0.1重量%であった。
(タック層組成物B)
 錫微粒子をポリグリセリン希釈液に対して重量%で0.5重量%になるようにした他はタック層Aと同様にして、タック層Bを作製した。金属微粒子(P)に対する金属微粒子(M)の割合は0.5重量%であった。
(タック層組成物C)
 錫微粒子をポリグリセリン希釈液に対して重量%で1重量%になるようにした他はタック層Aと同様にして、タック層Cを作製した。金属微粒子(P)に対する金属微粒子(M)の割合は1重量%であった。
(タック層組成物D)
 錫微粒子に替えて平均一次粒径1.75μmの錫ニッケル銅合金微粒子(三井金属鉱業株式会社製)を用いた他はタック層Aと同様にして、タック層Dを作製した。金属微粒子(P)に対する金属微粒子(M)の割合は0.1重量%であった。
(タック層組成物E)
 錫ニッケル銅合金微粒子をポリグリセリン希釈液に対して重量%で1重量%になるようにした他はタック層Dと同様にして、タック層Eを作製した。金属微粒子(P)に対する金属微粒子(M)の割合は1重量%であった。
(タック層組成物F)
 平均一次粒径2.0μmのビスマス合金微粒子(福田金属箔粉工業株式会社製)をポリグリセリン希釈液に対して重量%で0.5重量%になるようにした他はタック層Aと同様にして、タック層Fを作製した。金属微粒子(P)に対する金属微粒子(M)の割合は0.5質量%であった。
(タック層組成物G)
 錫微粒子をポリグリセリン希釈液に対して重量%で0.01重量%になるようにした他はタック層Aと同様にして、タック層Gを作製した。金属微粒子(P)に対する金属微粒子(M)の割合は0.01重量%であった。
(タック層組成物H)
 錫微粒子をポリグリセリン希釈液に対して重量%で2重量%になるようにした他はタック層Aと同様にして、タック層Hを作製した。金属微粒子(P)に対する金属微粒子(M)の割合は2重量%であった。
(タック層組成物I)
 金属微粒子を含まない他はタック層Aと同様にして、タック層Iを作製した。
[実施例1]
 そして、50℃に温めたホットプレート上で導電性接合層Aの上に上述のタック層組成物Aを乾燥後の膜厚が2μmとなるようにスプレーコート法で塗布し、50℃で180秒乾燥させ、タック層を形成した。このようにして、実施例1に係る接合フィルムを得た。
[実施例2~6、比較例1~5]
 同様にして、表1および表2に示す導電性接合層とタック層の組み合わせで、実施例2~6、比較例1~5に係る接合フィルムを得た。
[ウエハ加工用テープの作製]
 一方、次のようにして粘着フィルムを作製した。ブチルアクリレート65重量部、2-ヒドロキシエチルアクリレート25重量部、アクリル酸10重量部をラジカル重合させ、2-イソシアネートエチルメタクリレートを滴下反応させて合成した重量平均分子量80万のアクリル共重合体に硬化剤としてポリイソシアネート3重量部、光重合開始剤として1-ヒドロキシ-シクロヘキシル-フェニル-ケトン1重量部を加えて混合し、粘着剤層組成物とした。作製した粘着剤層組成物を乾燥膜厚が10μmとなるようにフィルム(基材フィルム以外の塗工用フィルム)に塗工し、120℃で3分間乾燥させた。この後、そのフィルムに塗工した粘着剤層組成物を、基材フィルムである厚さ100μmのポリプロピレン-エラストマー(PP:HSBR=80:20のエラストマー)樹脂フィルム上に転写させることで粘着フィルムを作製した。
 なお、ポリプロピレン(PP)は、日本ポリケム株式会社製のノバテックFG4を用い、水添スチレンブタジエン(HSBR)はJSR株式会社製のダイナロン1320Pを用いた。また、塗工用フィルムはシリコーン離型処理されたPETフィルム(帝人:ヒューピレックスS-314、厚み25μm)を用いた。
 その後、上記粘着フィルムの粘着剤層上に上記接合フィルムの導電性接合層を貼合しウエハ加工用テープを得た。
[サンプルの作製]
 半導体ウエハとして、厚み230μmの半導体ウエハの表面にTi/Au、Ti/Ag、Ti/Cu、Ti/Niの各種チップ電極層を形成したものを準備した。各種チップの厚みは100nmであった。また、基板として、厚みが1.2mmの調質が半硬質の無酸素銅板を準備した。上記実施例および比較例に係る接合フィルムを50℃に熱したホットプレート上に載置して加熱してタック層のタック性を高めた状態でタック層に、表1および表2に示す種類の電極の半導体ウエハの表面(半導体素子電極層側の面)を貼り付け、その後室温に戻し、タック層を冷却硬化させた状態でダイシング装置(DISCO社製、DAD340(商品名))を用いて、接合フィルムとともに7mm×7mmの半導体チップにダイシングした。その後、高圧水銀灯ランプの紫外線照射機を用いて、粘着フィルムの基材フィルム面側から照射量が200mJ/cm2となるように紫外線照射を行った。そして、ダイボンダ―(キヤノンマシナリー株式会社製、CPS-6820(商品名))を用いて粘着フィルムをエキスパンドし、その状態で半導体チップを接合フィルムとともにピックアップし、接合フィルムの導電性接合層側を基板上に載置した。
 その後、上述の半導体チップ、接合フィルム、基板の積層体を、導電性接合層を銅微粒子ペーストで形成したものは、300℃で60分間、銀微粒子ペーストで形成したものは、250℃で60分間、それぞれ加熱して、導電性接合層を焼結させ、20個の実装サンプルを作製した。
 実装サンプルについて、-55℃で30分間と200℃で30分間を1サイクルとする温度サイクル試験(TCT)を行った。100回ごとにサンプルを取り出し、割れ、剥離が無いか目視にて検査した。その後、超音波顕微鏡(日立建機株式会社製、Mi-Scope(商品名))とプローブ(型式「PQ2-13」、50MHz)を使用して、半導体チップ側から超音波を照射し、反射法で剥離の測定を行った。剥離面積が10%を超えたものを故障と判定した。本実施例および比較例に係る接合フィルムを用いた実装サンプルの故障と判定されるまでのTCT回数が2500~3000回であったものを優良品としてAで判定し、1000~2000回であったものを良品としてBで判定し、1000回以下であったものを不良品としてCde判定した。そして、全ての種類の電極との接合においてA判定を含みB判定以上であった接合フィルムを優良品として◎で評価し、全ての種類の電極との接合においてB判定であったものを良品として○で評価し、いずれかの電極との接合においてC判定であったものを不良品として×で評価した。その結果を表1,2に示す。
Figure JPOXMLDOC01-appb-T000001
 
Figure JPOXMLDOC01-appb-T000002
 
 実施例1~6は、表1に示すように、タック層が導電性接合層内の金属微粒子(P)に対して金属微粒子(M)を0.1~1.0重量%含むため、半導体素子の電極の種類によらず、基板との接合が良好であり、温度サイクル試験評価において良好な結果となった。
 これに対して、比較例1,2は、表2に示すように、タック層に金属微粒子(M)が含まれていないため、半導体素子の電極の種類によっては、基板との接合が良好ではなく、温度サイクル試験評価において劣る結果となった。比較例3は、金属微粒子(M)の融点が250℃を超えるため、電極との合金相が形成されないため、接合状態が良好ではなく、温度サイクル試験評価において劣る結果となった。比較例4は、金属微粒子(M)の含有割合が、金属微粒子(P)に対して0.01重量%と少ないため、接合後に金属多孔質体と半導体素子の電極との界面に金属微粒子(M)と電極との合金相が十分に形成されず、半導体素子の電極の種類によっては、基板との接合が良好ではなく、温度サイクル試験評価において劣る結果となった。比較例5は、金属微粒子(M)の含有割合が、金属微粒子(P)に対して2重量%と多いため、接合後に金属多孔質体と半導体素子の電極との界面に金属微粒子(M)と電極との合金相が厚く形成されすぎ、半導体素子の電極の種類によっては、基板との接合が良好ではなく、温度サイクル試験評価において劣る結果となった。
2:半導体素子
10:ウエハ加工用テープ
11:離型フィルム
12:粘着フィルム
12a:基材フィルム
12b:粘着剤層
13:接合フィルム
13a:導電性接合層
13b:タック層
40:基板
 

Claims (15)

  1.  半導体素子と基板とを接合するための接合フィルムであって、
     金属微粒子(P)を含む導電性ペーストがフィルム状に成形された導電性接合層と、
     タック性を有し、前記導電性接合層に積層されたタック層と
    を有し、
     前記タック層は、前記導電性接合層内の前記金属微粒子(P)に対して、金属微粒子(M)を0.1~1.0重量%含み、
     前記金属微粒子(M)は融点が250℃以下であることを特徴とする接合フィルム。
  2.  前記金属微粒子(P)は、平均一次粒径が10~500nmであることを特徴とする請求項1に記載の接合フィルム。
  3.  前記導電性ペーストは、有機溶剤(S)を含むことを特徴とする請求項1または2に記載の接合フィルム。
  4.  前記金属微粒子(P)は、銅または銀を含むことを特徴とする請求項1から請求項3のいずれか一項に記載の接合フィルム。
  5.  前記導電性ペーストは、有機バインダー(R)を含むことを特徴とする請求項1から請求項4のいずれか一項に記載の接合フィルム。
  6.  前記タック層は、ポリグリセリン、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ホスフィン類、ホスファイト類、スルフィド類、ジスルフィド類、トリスルフィド類、およびスルホキシド類の中から選択される1種もしくは2種以上からなることを特徴とする請求項1から請求項5のいずれか一項に記載の接合フィルム。
  7.  前記金属微粒子(M)は、平均一次粒径が1~3μmであることを特徴とする、請求項1から請求項6のいずれか一項に記載の接合フィルム。
  8.  前記金属微粒子(M)は、錫を含むことを特徴とする請求項1から請求項7のいずれか一項に記載の接合フィルム。
  9.  前記有機溶剤(S)は、常圧における沸点が100℃以上でかつ分子中に1または2以上のヒドロキシル基を有するアルコールおよび/もしくは多価アルコールからなる有機溶剤(SC)を含むことを特徴とする請求項3から請求項8のいずれか一項に記載の接合フィルム。
  10.  前記有機バインダー(R)は、セルロース樹脂系バインダー、アセテート樹脂系バインダー、アクリル樹脂系バインダー、ウレタン樹脂系バインダー、ポリビニルピロリドン樹脂系バインダー、ポリアミド樹脂系バインダー、ブチラール樹脂系バインダー、およびテルペン系バインダーの中から選択される1種または2種以上であることを特徴とする請求項5から請求項9のいずれか一項に記載の接合フィルム。
  11.  基材フィルムと該基材フィルム上に設けられた粘着剤層とを有する粘着フィルムと、
    請求項1から請求項10のいずれか一項に記載の接合フィルムとを有し、
    前記粘着剤層上に、前記接合フィルムの導電性接合層が設けられていることを特徴とするウエハ加工用テープ。
  12.  金属微粒子(P)を含む導電性ペーストがフィルム状に成形された導電性接合層と、タック性を有し金属微粒子(M)を含んで、前記導電性接合層に積層されたタック層とを有する接合フィルムを、半導体素子と基板と間に配置して加熱し、前記タック層が熱分解され、前記金属微粒子(M)が溶融して前記半導体素子の電極と反応した後に、前記導電性接合層の前記金属微粒子(P)を焼結させることによって、前記半導体素子と前記基板とを接合する接合工程を有することを特徴とする接合体の製造方法。
  13.  基板上に、金属多孔質体からなる導電接続部材を有し、その上に半導体素子を有する半導体と基板の接合体であって、
     請求項1から請求項10のいずれか一項に記載の接合フィルムを用いて接合されており、
     前記金属多孔質体は、請求項1から請求項10のいずれか一項に記載の接合フィルムに含まれる金属微粒子(P)の焼結体であり、
     前記金属多孔質体と前記半導体素子の電極との界面には、請求項1から請求項10のいずれか一項に記載の接合フィルムに含まれる金属微粒子(M)と前記電極との合金相または金属化合物相が形成されていることを特徴とする半導体と基板の接合体。  
  14.  前記金属多孔質体の空隙率が1~6体積%であり、平均空孔径が10~60nmであることを特徴とする請求項13に記載の半導体と基板の接合体。
  15.  基材フィルムと該基材フィルム上に設けられた粘着剤層とを有する粘着フィルムと、
     半導体素子と基板とを接合するための接合フィルムと、
     半導体ウエハとが貼合された貼合体であって、
     前記接合フィルムは、金属微粒子(P)を含む導電性ペーストがフィルム状に成形された導電性接合層と、タック性を有し、前記導電性接合層に積層されたタック層とを有し、
     前記導電性接合層が前記粘着剤層に貼合され、前記半導体ウエハは前記タック層に貼合されており、
     前記タック層は熱分解可能であり、かつ前記導電性接合層内の前記金属微粒子(P)に対して金属微粒子(M)を0.1~1.0重量%含み、
    接合時の加熱により、前記タック層が熱分解され、金属微粒子(M)が溶融して前記半導体素子の電極と反応した後に、
     前記導電性接合層の前記金属微粒子(P)が焼結することによって、前記半導体素子と前記基板とが接合されることを特徴とする貼合体。
     
     
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