WO2011142318A1 - 電子部品及びその製造方法 - Google Patents
電子部品及びその製造方法 Download PDFInfo
- Publication number
- WO2011142318A1 WO2011142318A1 PCT/JP2011/060658 JP2011060658W WO2011142318A1 WO 2011142318 A1 WO2011142318 A1 WO 2011142318A1 JP 2011060658 W JP2011060658 W JP 2011060658W WO 2011142318 A1 WO2011142318 A1 WO 2011142318A1
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- oxide
- powder
- mass
- parts
- conductor film
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- H01L2924/01322—Eutectic Alloys, i.e. obtained by a liquid transforming into two solid phases
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/013—Alloys
- H01L2924/014—Solder alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
- H01L2924/097—Glass-ceramics, e.g. devitrified glass
- H01L2924/09701—Low temperature co-fired ceramic [LTCC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1204—Optical Diode
- H01L2924/12044—OLED
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/14—Integrated circuits
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/151—Die mounting substrate
- H01L2924/156—Material
- H01L2924/15786—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
- H01L2924/15787—Ceramics, e.g. crystalline carbides, nitrides or oxides
Definitions
- the present invention relates to an electronic component including a conductive film that does not include wet plating and a method for manufacturing the same.
- the present invention also relates to a material for forming the conductor film.
- a conductor film (wiring, electrode, etc.) having a predetermined pattern is formed on a substrate (for example, a ceramic substrate) used for constructing an electronic component (typically including a semiconductor element) such as a hybrid IC or a multichip module.
- a substrate for example, a ceramic substrate
- an electronic component typically including a semiconductor element
- a conductive film-forming material hereinafter referred to as a conductive film-forming material (composition) having such fluidity) prepared in a paste form (or a slurry form or an ink form) containing a powder material constituting the film is used. "Conductive paste" is used.
- a conductive paste for example, powdered Ag or an Ag-based alloy (eg, Ag—Pd alloy, Ag—Pt alloy), which is a main component for forming a conductor, and various additives added as necessary (for example, Examples thereof include those prepared by dispersing an inorganic oxide, glass powder, and the like) in a predetermined organic medium (vehicle) (hereinafter abbreviated as “Ag-based paste”).
- Ag-based paste powdered Ag or an Ag-based alloy (eg, Ag—Pd alloy, Ag—Pt alloy), which is a main component for forming a conductor, and various additives added as necessary (for example, Examples thereof include those prepared by dispersing an inorganic oxide, glass powder, and the like) in a predetermined organic medium (vehicle) (hereinafter abbreviated as “Ag-based paste”).
- Ag-based paste a predetermined organic medium
- Patent Document 1 describes an example of this type of conductor paste.
- connection strength cannot be obtained between the bonding wire and the conductor film. If the connection strength is weak, problems such as peeling of the bonding wire at the bonding part may occur, and the connection reliability cannot be sufficiently ensured.
- connection strength wire bonding property
- an inorganic base material a conductor film formed on the surface of the base material, and a bonding wire bonded to a part of the conductor film, at least partly a wire
- An electronic component in which a bonding portion is formed is provided.
- at least a portion of the conductor film that forms the wire bonding portion includes an Ag-based metal made of Ag or an Ag-based alloy, and aluminum (Al) coating the Ag-based metal.
- the coating amount of the metal oxide is an amount corresponding to 0.02 to 0.1 parts by mass with respect to 100 parts by mass of the Ag-based metal.
- “electronic component” means an inorganic base material (typically a crystalline (ie, non-glass) ceramic base material or an amorphous ceramic base material (ie, a glass ceramic base material). )) In general. Accordingly, hybrid ICs, multichip modules, ceramic capacitors, and the like having such an inorganic base material are typical examples included in the “electronic component” defined in this specification.
- the conductor film of at least the portion forming the wire bonding portion of the conductor film formed on the surface of the inorganic base material has the above configuration (component)
- the conventional conductor film Compared to the above, it has better wire bonding properties. Therefore, in such an electronic component, wire bonding (connection) between the elements (chips) to be wire bonded such as semiconductor elements and the conductor film with sufficient connection strength (particularly the strength of the connection portion between the conductor film and the bonding wire). Is realized.
- the conductor film that forms the wire bonding portion further includes an inorganic oxide and / or oxide glass as an additive.
- the sinterability of the conductor film is increased, and the mechanical connection strength (that is, wire bondability) at the wire bonding portion between the conductor film and the bonding wire can be further improved.
- the conductor film of this structure is excellent in solder heat resistance, when a conductor film other than the wire bonding part, for example, a conductor film for mounting a semiconductor chip or the like is formed, the semiconductor chip or the like is mounted on the substrate. It is possible to effectively prevent the occurrence of solder cracks when performing (attaching).
- an inorganic oxide is included as the additive, and the inorganic oxide is a mixture of bismuth oxide and copper oxide.
- the amount of the mixture added is 0.1% with respect to 100 parts by mass of the Ag-based metal.
- An amount corresponding to 5 to 5 parts by mass is preferable.
- oxide glass is included as the additive, and the addition amount of the glass is preferably an amount corresponding to 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the Ag-based metal.
- the inorganic base material is a crystalline ceramic base material made of crystalline ceramics, and at least a portion of the conductor film that forms the wire bonding portion is An inorganic oxide is included as the additive.
- the inorganic base material is an amorphous ceramic base material made of an amorphous ceramic containing a glass component as a main component. At least the portion that forms the wire bonding portion includes oxide glass as the additive.
- the main component means a component in an amount exceeding 50% by mass of the whole, typically 70% by mass or more.
- the bonding wire is made of a metal whose main component is any one of gold, aluminum, and copper.
- a bonding wire made of such a metal material can be suitably used, for example, for electrically and mechanically connecting a semiconductor element and a conductor film.
- the conductor paste for forming a wire bonding portion for use in an application for forming a conductor film having at least a wire bonding portion in an electronic component in which the wire bonding portion is formed. That is, the conductor paste for forming a wire bonding portion disclosed herein has an average particle size (typically an average particle size obtained based on an electron microscope observation or a light scattering method) made of Ag or an Ag-based alloy is 0.
- Ag-based metal powder (metal fine particles) and any one selected from the group consisting of Al, Zr, Ti, Y, Ca, Mg and Zn that coats the surface of the Ag-based metal powder. It contains an organic metal compound or metal oxide as a constituent element.
- the coating amount of the organic metal compound or metal oxide is an amount corresponding to 0.02 to 0.1 parts by mass in terms of metal oxide with respect to 100 parts by mass of the Ag metal powder.
- the inorganic oxide powder and / or oxide glass powder are further included as an additive.
- a conductor paste using an Ag-based metal powder having an average particle size of 3.0 to 6.0 ⁇ m as the Ag-based metal powder and containing an inorganic oxide powder and / or an oxide glass powder as an additive is preferable.
- a conductor film with improved wire bonding properties can be formed.
- the conductor film formed using the conductor paste of such a structure is excellent in solder heat resistance, when a conductor film other than the wire bonding portion, for example, a conductor film for mounting a semiconductor chip or the like is formed, the semiconductor chip It is possible to effectively prevent the occurrence of solder breakage when mounting (attaching) or the like on the substrate.
- an inorganic oxide powder is included as the additive, and the inorganic oxide powder is a mixture of bismuth oxide and copper oxide, and the addition amount of the mixture is 100 parts by mass of the Ag-based metal powder.
- the amount corresponding to 0.5 to 5 parts by mass is preferable.
- oxide glass powder is included as the additive, and the addition amount of the glass powder is an amount corresponding to 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the Ag-based metal powder. Is preferred.
- At least in part comprising an inorganic base material, a conductor film formed on the surface of the base material, and a bonding wire bonded to a part of the conductor film
- a method for manufacturing an electronic component having a wire bonding portion is provided.
- the method of manufacturing an electronic component disclosed herein includes (1) the following components: an Ag-based metal powder having an average particle size of 0.3 to 6.0 ⁇ m made of Ag or an Ag-based alloy; and the above Ag-based metal An organic metal compound or metal oxide comprising any one selected from the group consisting of Al, Zr, Ti, Y, Ca, Mg and Zn which coats the surface of the powder;
- the coating amount of the organic metal compound or the metal oxide is an amount corresponding to 0.02 to 0.1 parts by mass in terms of metal oxide with respect to 100 parts by mass of the Ag metal powder; (2) applying the conductor paste to the surface of the inorganic substrate to form a conductor film on the surface of the inorganic substrate; and (3) Bonding the bonding wire to a part of the formed conductor film.
- the conductor film formed on the surface of the inorganic base material is formed from the conductor paste for forming the wire bonding portion having the above-described configuration. It has sex. For this reason, sufficient connection strength is realized in the bonding portion (that is, the wire bonding portion) between the conductor film and the bonding wire. That is, by this manufacturing method, an electronic component having good connectivity with a semiconductor element or the like and excellent in electrical characteristics and mechanical characteristics can be manufactured.
- the conductor paste further includes an inorganic oxide powder and / or an oxide glass powder as an additive.
- an inorganic oxide powder and / or an oxide glass powder as an additive.
- a conductor paste using an Ag-based metal powder having an average particle size of 3.0 to 6.0 ⁇ m as the Ag-based metal powder and containing an inorganic oxide powder and / or an oxide glass powder as an additive is preferable. .
- an inorganic oxide powder is included as the additive, and the inorganic oxide powder is a mixture of bismuth oxide and copper oxide, and the addition amount of the mixture is 100 parts by mass of the Ag-based metal powder.
- the amount corresponding to 0.5 to 5 parts by mass is preferable.
- oxide glass powder is included as the additive, and the addition amount of the glass powder is an amount corresponding to 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the Ag-based metal powder. Is preferred.
- the inorganic base material is a crystalline ceramic base material
- the conductor paste includes an inorganic oxide powder as the additive.
- the inorganic base material is an amorphous ceramic base material mainly composed of a glass component, and the conductor paste is used as the additive. It contains an oxide glass powder.
- FIG. 1 is a perspective view schematically showing an external appearance of an electronic component according to an embodiment.
- FIG. 2 is a photograph showing a surface structure of an electronic component according to one embodiment.
- FIG. 3 is an explanatory view showing a test method of a wire bonding property evaluation test.
- FIG. 4 is a photograph showing the state of the test piece surface after the test piece according to Example 4 is immersed in molten solder.
- FIG. 5 is a photograph showing the state of the test piece surface after the test piece according to Example 1 is immersed in molten solder.
- FIG. 6 is a photograph showing the state of the test piece surface after the test piece according to Example 13 is immersed in molten solder.
- the conductor paste for forming a wire bonding portion according to the present invention is a wire bonding portion forming paste characterized by having an Ag-based metal powder as a main component, As long as the above can be achieved, the content and composition of other subcomponents are not particularly limited.
- the Ag-based metal powder is a group of fine particles substantially composed of Ag or an Ag-based alloy (for example, Ag—Au alloy, Ag—Pd alloy).
- an Ag-based metal powder from the viewpoint of imparting electrical conductivity, Ag alone or a specific resistance value is approximately 1.8 to 5.0 ⁇ 10 ⁇ 6 ⁇ ⁇ cm (preferably 1.9 to 3.0 ⁇ 10 ⁇ An alloy of 6 ⁇ ⁇ cm, for example 2.2 ⁇ 10 ⁇ 6 ⁇ ⁇ cm) is suitable. Further, although not particularly limited, an Ag-based metal powder having an average particle diameter of 0.3 to 6.0 ⁇ m is preferable. In addition, an Ag-based metal powder having a relatively narrow average particle size and a relatively narrow particle size distribution that does not substantially include particles having a particle size of 10 ⁇ m or more (particularly preferably a particle size of 8 ⁇ m or more) is provided. Particularly preferred.
- a conductor paste is produced using an Ag-based metal powder having an average particle size of 3.0 ⁇ m or more (typically 3.0 to 6.0 ⁇ m) as the Ag-based metal powder It is preferable to use (include) an additive such as an inorganic oxide powder or glass powder to be described later for the conductor paste.
- the Ag-based metal powder itself may be produced by a conventionally known production method and does not require special production means. For example, an Ag-based metal powder produced by a known reduction precipitation method, gas phase reaction method, gas reduction method, or the like can be used.
- the organic metal compound used for coating the Ag-based metal powder is a metal (including a metal oxide or a reduced product thereof) suitable for realizing the object of the present invention on the surface of the Ag-based metal powder (after firing).
- Suitable constituent metal elements include Al, Zr, Ti, Y, Ca, Mg, Zn, or the like.
- Organic acid metal salts, metal alkoxides or chelate compounds containing these as constituent elements are preferably used.
- suitable metal alkoxides include zirconium alkoxides such as zirconium ethoxide and zirconium butoxide, aluminum ethoxide (Al (OC 2 H 5 ) 3 ), aluminum t-butoxide (Al (OC (CH 3 ) 3 ) 3 ).
- titanium (IV) alkoxides such as tetrapropoxy titanium (Ti (OC 3 H 7 ) 4
- Ti (OC 3 H 7 ) 4 titanium alkoxides
- Suitable chelate compounds include ethylenediamine (en) complexes and ethylenediaminetetraacetato (edta) complexes having Zn, Mg, Ca, etc. as the central metal atom (ion).
- a so-called chelate resin in which a chelate is formed with a metal (ion) such as Ti, Zn, or Mg is also suitable as the organic metal compound (chelate compound) according to the present invention.
- organic metal compounds used for coating of Ag-based metal powder are organic compounds containing Al, Zr, Ti, Y, Ca, Mg, Zn, or the like as a constituent metal element. It is an acid metal salt.
- an organic acid metal salt containing Al or Zr as a main constituent metal element is suitable.
- Particularly preferred organic acid metal salts are carboxylates having the above-listed elements as the main constituent metal elements.
- compounds of Al, Ca, Ti, Y or Zr and various fatty acids for example, naphthenic acid, octylic acid, ethylhexanoic acid), abietic acid, naphthoic acid and other organic acids can be mentioned.
- Particularly suitable organic acid metal salts are compounds of Al or Zr and carboxylic acids (particularly fatty acids).
- a film of a metal oxide (zirconia, alumina, etc.) that is an oxide of the organic metal compound is formed on the surface of the Ag metal powder.
- a metal oxide can be produced by firing an Ag-based metal powder coated with an inorganic substrate (for example, a crystalline ceramic substrate or an amorphous ceramic substrate). Accordingly, it is not an essential treatment that the Ag-based metal powder coated with the organic metal compound (that is, the paste containing the Ag-based metal powder) is preliminarily heat-treated before being attached to the inorganic substrate.
- various oxide sols may be used as the coating material for the Ag-based metal powder of the present invention instead of the organic metal compound.
- the surface of the Ag-based metal powder is directly coated with a metal compound (oxide) such as zirconia or alumina.
- the conductor film formed of the Ag-based metal powder coated with the organic metal compound or the metal oxide having the above-described composition is not fired (if the organic metal compound is coated, the metal In particular, high wire bondability, solder heat resistance, and solder weather resistance (solderability) are realized. Therefore, when the Ag paste according to the present invention is used, a practically sufficient level of wire bonding property and solder heat resistance can be obtained without using a large amount of expensive noble metal such as palladium (Pd) and without performing complicated plating treatment.
- a conductive film (for example, a surface conductor film, a side conductor film, or an internal conductor film) having a property, adhesive strength, and solder weather resistance can be formed on an inorganic substrate (for example, an amorphous ceramic substrate).
- an organic medium in which the metal powder is dispersed
- such an organic vehicle may be any material in which metal powder is dispersed, and those used in conventional conductor pastes can be used without particular limitation.
- examples thereof include cellulose polymers such as ethyl cellulose, high-boiling organic solvents such as ethylene glycol and diethylene glycol derivatives, toluene, xylene, mineral spirits, butyl carbitol, and terpineol.
- the conductor paste of the present invention can contain various additives as subcomponents as long as the original wire bonding property, solder wettability, solder heat resistance, solder weather resistance and the like of the paste are not significantly impaired.
- the additive include inorganic oxide powder and glass powder.
- addition of some inorganic oxide powder and / or glass powder is preferred.
- the inorganic oxide powder can contribute to the improvement of the adhesive strength between the inorganic substrate (for example, a crystalline ceramic substrate) and the conductor film. Furthermore, it is possible to prevent excessive firing shrinkage stress during firing of the conductor film formed from the conductor paste of the present invention, and to maintain the accuracy and mechanical strength of the electronic component to be manufactured at a practically high level.
- bismuth oxide is a particularly suitable inorganic oxide because it promotes the sintering of the Ag-based metal powder and can reduce the viscosity of the conductor paste to improve the wettability with the inorganic base material.
- copper oxide can improve adhesiveness with an inorganic base material (board
- the average particle size is 5 ⁇ m or less (typically 1 to 5 ⁇ m, particularly preferably 1 ⁇ m or less, from the viewpoint of optimizing the filling rate and dispersibility of the paste. ) Is preferred.
- the specific surface area is preferably at least 0.5 m 2 / g, preferably 1.0 m 2 / g or more (typically 1.0 to 2.0 m 2 / g, particularly preferably 2.0 m 2 / g). Particular preference is given to powders of ⁇ 100 m 2 / g).
- glass powder is an inorganic component (inorganic binder) that contributes to stable baking (fixing of adhesive strength) of paste components attached on an inorganic substrate (for example, an amorphous ceramic substrate).
- inorganic substrate for example, an amorphous ceramic substrate.
- Oxide glass is particularly preferable. A softening point of approximately 800 ° C. or less is preferable from the relationship with the firing temperature described later.
- glass powders include lead-based, zinc-based, borosilicate-based glasses, and glasses containing alkaline earth metal oxides, and typically include PbO—SiO 2 —B 2 O 3 based glasses.
- the glass powder to be used preferably has a specific surface area of about 0.5 to 50 m 2 / g, and particularly preferably has an average particle size of 2 ⁇ m or less (particularly about 1 ⁇ m or less).
- the conductor paste of the present invention can contain various organic additives as subcomponents as long as the original wire bonding property, solder wettability, solder heat resistance, solder weatherability, etc. of the paste are not significantly impaired.
- organic additives include various organic binders, various coupling agents such as silicon-based, titanate-based, and aluminum-based for the purpose of improving adhesion to an inorganic substrate (for example, a crystalline ceramic substrate).
- the organic binder include those based on acrylic resin, epoxy resin, phenol resin, alkyd resin, cellulosic polymer, polyvinyl alcohol and the like.
- the conductor paste of this invention with favorable viscosity and a coating-film (adhesion film
- various photopolymerizable compounds and photopolymerization initiators may be appropriately added.
- a surfactant, an antifoaming agent, a plasticizer, a thickener, an antioxidant, a dispersant, a polymerization inhibitor, and the like may be added as appropriate to the conductor paste according to the present invention. it can.
- These additives may be any additives that can be used for the preparation of conventional conductor pastes, and will not be described in detail.
- the inorganic base material used in the method of manufacturing an electronic component disclosed herein includes a crystalline ceramic base material (hereinafter referred to as “ceramic base material”) and an amorphous ceramic base material mainly composed of a glass component. Material (hereinafter referred to as “glass ceramic substrate”).
- the glass ceramic substrate is a substrate formed by firing a green sheet containing a glass component as a main component and a filler (ceramic powder such as alumina).
- a glass component include silicon oxide, strontium oxide, calcium oxide, and aluminum oxide (alumina).
- the filler cordierite, mullite, steatite, forsterite or the like having a relative dielectric constant of 30 or less can be used.
- the mass ratio of the glass component to the filler is preferably 60:40 to 80:20 (for example, 70:30).
- a green sheet is prepared by mixing a glass component, a filler (for example, alumina), and a binder together with an organic solvent to prepare a slurry-like dielectric paste, which is a support such as a polyethylene terephthalate (PET) sheet. It is formed by forming a film on the top by a doctor blade method or the like.
- a conventionally well-known binder can be used without a restriction
- a conventionally well-known organic solvent can also be used without a restriction
- the manufacturing method of the electronic component of this invention is demonstrated.
- a method for coating the surface of an Ag metal powder with an organic metal compound or a metal oxide thereof that is, a method for producing a metal powder coated with a predetermined organic metal compound
- the surface of the main Ag-based metal powder is uniformly and uniformly coated with the organic metal compound or the metal oxide, but the coating method is not particularly limited. Absent.
- conventionally known methods for coating organic particles on metal particles can be applied as they are.
- a desired organic metal compound is dissolved or dispersed in an appropriate organic solvent such as toluene, xylene, or various alcohols.
- the coating amount of the organic metal compound or the metal oxide thereof is 0.02 to 0.1 parts by mass (100 parts by mass of the Ag metal powder in terms of oxide) ( For example, a desired organic metal compound or metal oxide is coated on the Ag metal powder so as to be an amount corresponding to 0.025 to 0.1 parts by mass).
- the coating amount is too small in terms of oxide, the amount corresponding to 0.02 parts by mass with respect to 100 parts by mass of the Ag-based metal powder, the effect of the coating is diminished and the above-described object relating to the present invention is achieved. It is hard to do.
- the coating amount is excessively larger than the amount corresponding to 0.1 parts by mass with respect to 100 parts by mass of the Ag-based metal powder in terms of oxide, various properties such as the original electrical characteristics of the Ag-based metal powder are obtained. This is not preferable because the function may be impaired.
- This conductor paste can be easily prepared by mixing an Ag metal powder (typically Ag alone) coated with an organic metal compound or its metal oxide and an organic medium (vehicle) as described above. Can do.
- an additive additive as described above may be added and mixed as necessary. For example, using a three-roll mill or other kneader, the Ag-based metal powder and various additives (additives) are directly mixed together with the organic vehicle at a predetermined blending ratio and kneaded together.
- the content of the Ag-based metal powder coated with one or more organic metal compounds or metal oxides thereof is 60 to 95% by mass of the entire paste.
- the respective materials are preferably kneaded and particularly preferably kneaded so as to be 70 to 90% by mass.
- the amount of the organic vehicle used for preparing the paste is suitably about 1 to 40% by mass of the entire paste, and particularly preferably 1 to 20% by mass.
- the above-described inorganic oxide powder is added as an additive, it is preferable to use about 0.5 to 5 parts by mass with respect to 100 parts by mass of the Ag-based metal powder. More preferably, it is about 0.5 to 3 parts by mass. More preferably, it is about 1 to 2 parts by mass.
- the sintered paste obtained from the paste of the present invention (conductor film) with respect to the inorganic base material without substantially impairing the good conductivity and solder wettability of the conductor paste according to the present invention. Improvement of adhesive strength and suppression of firing shrinkage, and further improvement of wire bonding property and solder heat resistance can be realized.
- a ceramic base material as an inorganic base material
- inorganic oxide powder it is preferable to add to a conductor paste.
- the glass powder is added as an additive, it is preferably used in an amount of about 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the Ag-based metal powder.
- a glass ceramic substrate green sheet
- a conductor containing an inorganic metal oxide powder and / or an oxide glass powder as an additive using a metal powder having an average particle size of 3.0 to 6.0 ⁇ m as an Ag-based metal powder A paste can be preferably used.
- the above prepared conductor paste (conductor paste for forming the wire bonding part) is applied to an inorganic base material, which is conventionally used to form a conductor film such as wiring and electrodes on the inorganic base material. It can be handled in the same manner as the conductor paste that has been produced, and conventionally known methods can be employed without any particular limitation.
- the conductor paste is applied to the inorganic substrate so as to have a desired shape and thickness by a screen printing method, a dispenser application method, or the like.
- a heater typically a maximum calcination temperature of about 500 to 960 ° C., preferably a temperature range not exceeding the melting point of Ag, for example 700 to 960 ° C., particularly 800 to
- the applied paste is baked (baked) and cured by heating at 900 ° C. for a predetermined time.
- a target conductor film (wiring, electrode, etc.) is formed.
- the ceramic substrate is fired in advance, a conductor paste is applied onto the fired ceramic substrate, and the conductor It is preferable to perform a process (post-bake) for baking the paste.
- the target conductor film is formed on the ceramic substrate.
- a glass ceramic substrate is used as the inorganic substrate, it is preferable to apply a conductive paste on the green sheet and to fire the green sheet and the conductive paste (simultaneous baking). Thereby, the target conductor film is formed on the glass ceramic base material formed by firing the green sheet.
- a semiconductor chip or the like is mounted on the inorganic substrate (for example, solder mounting is performed by a reflow method).
- the mounted semiconductor chip typically an aluminum electrode (bonding pad) on the semiconductor chip
- a conductor film typically wiring or electrode
- Electronic components can be obtained by electrical and mechanical connection by the above method (that is, wire bonding).
- the conductor film formed from the conductor paste of the present invention can directly connect a semiconductor element or the like and the conductor film with a bonding wire without plating the surface of the conductor film as in the prior art.
- connection part (wire bonding part) of a conductor film and a bonding wire has sufficient connection strength (wire bonding property).
- a bonding wire similar to the conventional one used for wire bonding can be used.
- a metal wire whose main component is any metal element of gold, aluminum, and copper can be used.
- the conductor film formed with the conductor paste according to the present invention is excellent in solder heat resistance and solder weather resistance, it is preferably used when various semiconductor elements are mounted on the conductor film by solder. Can do.
- FIG. 1 is a perspective view schematically showing an external appearance of an electronic component according to an embodiment.
- an electronic component 10 according to this embodiment includes a glass ceramic substrate (inorganic substrate) 20, a conductor film 30 formed on the surface of the substrate 20, and a part of the conductor film 30. And a bonding wire 50 bonded to each other.
- the glass ceramic substrate 20 is a multilayer glass ceramic substrate in which a plurality of glass ceramic substrates on which a conductor film (inner conductor film) having a predetermined pattern is formed are laminated. Further, a via-hole conductor film (not shown) necessary for connecting the circuits in the vertical direction across the plurality of layers is formed.
- a conductor film 30 (typically, wiring and electrodes) having a predetermined pattern is formed on the surface of the ceramic substrate 20, and semiconductor elements 60 and 65 are solder-mounted on a part of the conductor film 30 by a reflow method. Yes.
- a plurality of bonding pads (typically aluminum electrodes) 70 formed on the semiconductor element 60 and the conductor film 30 are mechanically and electrically connected to each other by bonding wires 50.
- the bonding pad 75 of the semiconductor element 65 and the conductor film 30 are connected by the bonding wire 55.
- a connection with sufficient mechanical connection strength (wire bonding property) is realized at the portion where the conductor film 30 and the bonding wires 50 and 55 are connected, that is, the wire bonding portions 40 and 45. Yes.
- Example 1 a substantially spherical Ag powder having an average particle diameter of 0.7 ⁇ m prepared by a general wet method was used as the base of the metal powder.
- zirconium alkoxide here, zirconium butoxide
- the metal alkoxide was added to an appropriate organic solvent (in this case, methanol) to prepare a coating solution having a concentration of 5 to 100 g / l.
- an appropriate amount of the above Ag powder was suspended in the solution, and the suspension was maintained for 1 to 3 hours with appropriate stirring. Thereafter, the Ag powder was recovered and dried by ventilation at 60 to 110 ° C.
- the Ag powder (hereinafter referred to as “Zr coating Ag”) whose surface is almost uniformly coded by the zirconium alkoxide in an amount of 0.05 part by mass with respect to 100 parts by mass of the Ag powder in terms of zirconium oxide (ZrO 2 ). Powder "). )
- a conductor paste was prepared using the Zr-coated Ag powder obtained above. That is, the materials used were weighed so that the final paste concentration (weight ratio) was 87 wt% Zr-coated Ag powder and the balance was a vehicle (here, terpineol and ethyl cellulose), and kneaded using a three-roll mill. In this way, a conductor paste according to Example 1 was prepared.
- a conductor film was formed on the surface of a ceramic substrate (here, a ceramic (antenna module) substrate having a thickness of about 0.8 mm). That is, after the ceramic substrate is previously fired at 900 ° C. for 1 hour in an electric furnace, a conductor paste is applied to the surface of the ceramic substrate that has been fired based on a general screen printing method. Application was performed to form a coating film having a predetermined film thickness. Then, the drying process for 15 minutes was performed at 100 degreeC using the far-infrared dryer. By this drying treatment, the solvent was volatilized from the coating film, and an unfired conductor film was formed on the ceramic substrate.
- a ceramic substrate here, a ceramic (antenna module) substrate having a thickness of about 0.8 mm. That is, after the ceramic substrate is previously fired at 900 ° C. for 1 hour in an electric furnace, a conductor paste is applied to the surface of the ceramic substrate that has been fired based on a general screen printing method. Application was performed
- this conductor film was fired together with the ceramic substrate (post-baking). That is, the baking process was performed at a temperature of 800 ° C. for 45 minutes in an electric furnace. By this firing treatment, as shown in FIG. 2, a conductor film having a fired film thickness of 12 ⁇ m was baked on the ceramic substrate.
- the term “conductor film” refers to the conductor film after firing.
- an electronic component according to Example 1 including a bonding wire bonded to a part of a conductor film baked on a ceramic base material was produced.
- Example 2 An electronic component according to Example 2 was produced in the same manner as in Example 1 except that baking (post-baking) was performed at 850 ° C. for 45 minutes in an electric furnace.
- Example 3 A baking process (post-baking) was performed at 900 ° C. for 45 minutes in an electric furnace, and a conductive film having a fired film thickness of 12 ⁇ m was baked on the ceramic substrate.
- an electronic component according to Example 3 was manufactured in the same manner as Example 1.
- Example 4 A substantially spherical Ag powder having an average particle size of 2.0 ⁇ m was used. Then, the same treatment as Example 1 to obtain a Ag powder whose surface is substantially uniformly coated with zirconium alkoxide at a quantity corresponding to 0.1 parts by mass with respect to 100 parts by mass of the Ag powder in terms of ZrO 2. The materials used were weighed so that the final paste concentration (weight ratio) was 87 wt% of Zr-coated Ag powder and the balance was a vehicle (in this case, terpineol and ethyl cellulose), and 0.5 mass with respect to 100 parts by mass of Ag powder.
- a vehicle in this case, terpineol and ethyl cellulose
- Example 4 Part of bismuth oxide (Bi 2 O 3 ) and an amount of copper oxide (Cu 2 O) of 0.5 parts by mass with respect to 100 parts by mass of Ag powder, and mixed using a three-roll mill. Smelted. In this way, a conductor paste according to Example 4 was prepared. Using the conductor paste according to Example 4, firing treatment (post-baking) was performed at 850 ° C. for 45 minutes in an electric furnace, and a conductor film having a fired film thickness of 13 ⁇ m was baked on the ceramic substrate. In other respects, an electronic component according to Example 4 was produced in the same manner as Example 1.
- Example 5 A substantially spherical Ag powder having an average particle size of 2.5 ⁇ m was used. Then, the same treatment as Example 1 to obtain a Ag powder whose surface is substantially uniformly coated with zirconium alkoxide at a quantity corresponding to 0.05 parts by mass with respect to 100 parts by mass of the Ag powder in terms of ZrO 2. The materials used were weighed so that the final paste concentration (weight ratio) was 87 wt% of Zr-coated Ag powder and the balance was a vehicle (in this case, terpineol and ethyl cellulose), and 0.1 mass with respect to 100 mass parts of Ag powder.
- a vehicle in this case, terpineol and ethyl cellulose
- a part amount of oxide glass powder (Si—Zn—RO-based glass containing SiO 2 , ZnO, B 2 O 3 and BaO) was added and kneaded using a three-roll mill. Thereby, a conductor paste according to Example 5 was prepared.
- a conductor film was formed on the surface of the green sheet using the conductor paste according to Example 5. That is, a conductive paste was applied to the surface of the green sheet based on a general screen printing method to form a coating film having a predetermined film thickness. Then, the drying process for 15 minutes was performed at 100 degreeC using the far-infrared dryer.
- the green sheet used in this example was formed as follows. That is, a glass composed mainly of strontium oxide, calcium oxide, alumina and silicon oxide and an alumina ceramic powder as a filler are weighed so as to have a mass ratio of 70:30 and mixed with ethyl cellulose and terpineol to form a slurry.
- a dielectric paste was prepared, and the paste was applied onto PET so as to have a thickness of 40 ⁇ m by the doctor blade method.
- this conductor film was fired together with the green sheet (simultaneous firing). That is, the baking process was performed at 900 ° C. for 1 hour in an electric furnace. By this firing treatment, the green sheet was sintered to form a glass ceramic substrate, and the conductor film was baked on the glass ceramic substrate. The fired film thickness at this time was 13 ⁇ m.
- wire bonding was performed on a part of the conductor film formed on the glass ceramic substrate under the same conditions as in Example 1 to produce an electronic component according to Example 5.
- Example 6 Ag powder whose surface was coated almost uniformly with zirconium alkoxide in an amount of 0.025 parts by mass with respect to 100 parts by mass of Ag powder in terms of ZrO 2 was used. Otherwise, the electronic component according to Example 6 was manufactured in the same manner as Example 5.
- Example 7 A substantially spherical Ag powder having an average particle size of 0.4 ⁇ m was used. Then, the same treatment as Example 1 to obtain a Ag powder whose surface is substantially uniformly coated with zirconium alkoxide at a quantity corresponding to 0.1 parts by mass with respect to 100 parts by mass of the Ag powder in terms of ZrO 2. The materials used were weighed so that the final paste concentration (weight ratio) was 87 wt% of Zr-coated Ag powder and the balance was a vehicle (in this case, terpineol and ethyl cellulose), and 0.2 mass relative to 100 mass parts of Ag powder.
- a vehicle in this case, terpineol and ethyl cellulose
- Example 7 A part amount of oxide glass powder (Si—Zn—RO-based glass containing SiO 2 , ZnO, B 2 O 3 and BaO) was added and kneaded using a three-roll mill. In this way, a conductor paste according to Example 7 was prepared. Using the conductor paste according to Example 7, firing treatment (simultaneous firing) was performed at 850 ° C. for 1 hour in an electric furnace, and a conductor film having a fired film thickness of 15 ⁇ m was baked on the glass ceramic substrate. In other respects, an electronic component according to Example 7 was fabricated in the same manner as Example 3.
- Example 8 A conductor paste according to Example 8 was prepared in the same manner as Example 7 except that the oxide glass powder was not added in the paste preparation. Using the conductor paste according to Example 8, firing treatment (post-baking) was performed at 850 ° C. for 45 minutes in an electric furnace, and a conductor film having a fired film thickness of 15 ⁇ m was baked on the ceramic substrate. In other respects, an electronic component according to Example 8 was fabricated in the same manner as Example 1.
- Example 9 A paste containing bismuth oxide (Bi 2 O 3 ) and copper oxide (Cu 2 O) as an inorganic oxide was prepared. Bismuth oxide in an amount of 0.5 parts by mass with respect to 100 parts by mass of Ag powder and copper oxide in an amount of 0.5 parts by mass with respect to 100 parts by mass of Ag powder were used. For other points, a conductor paste according to Example 9 was prepared in the same manner as Example 8. The conductor paste according to Example 9 was used. Otherwise, the electronic component according to Example 9 was manufactured in the same manner as Example 8.
- Example 10 A substantially spherical Ag powder having an average particle size of 3.5 ⁇ m was used. Then, the same treatment as Example 1 to obtain a Ag powder whose surface is substantially uniformly coated with zirconium alkoxide at a quantity corresponding to 0.1 parts by mass with respect to 100 parts by mass of the Ag powder in terms of ZrO 2. The materials used were weighed so that the final paste concentration (weight ratio) was 87 wt% of Zr-coated Ag powder and the balance was vehicle (terpineol and ethyl cellulose), and kneaded using a three-roll mill. In this way, a conductor paste according to Example 10 was prepared.
- Example 10 using the conductor paste according to Example 10 and the same ceramic substrate as in Example 1, a conductor film was formed on the surface of the ceramic substrate. That is, based on a general screen printing method, a conductive paste was applied to the surface of a ceramic substrate to form a coating film having a predetermined film thickness. Then, the drying process for 15 minutes was performed at 100 degreeC using the far-infrared dryer. Next, this conductor film was fired together with the ceramic substrate (simultaneous firing). That is, a baking treatment was performed at 850 ° C. to 900 ° C. for 1 hour in an electric furnace. By this firing treatment, a conductor film having a fired film thickness of 14 ⁇ m was baked on the ceramic substrate. In other respects, an electronic component according to Example 10 was fabricated in the same manner as Example 1.
- Example 11 A paste containing bismuth oxide (Bi 2 O 3 ) and copper oxide (Cu 2 O) as an inorganic oxide was prepared. Bismuth oxide in an amount of 0.5 parts by mass with respect to 100 parts by mass of Ag powder and copper oxide in an amount of 0.5 parts by mass with respect to 100 parts by mass of Ag powder were used (added). In other respects, an electronic component according to Example 11 was produced in the same manner as Example 10.
- Example 12 A substantially spherical Ag powder having an average particle diameter of 6.0 ⁇ m was used. Then, the same treatment as Example 1 to obtain a Ag powder whose surface is substantially uniformly coated with zirconium alkoxide at a quantity corresponding to 0.05 parts by mass with respect to 100 parts by mass of the Ag powder in terms of ZrO 2. For other points, a conductor paste according to Example 12 was prepared in the same manner as Example 11. Using the conductor paste according to Example 12, firing treatment (simultaneous firing) was performed at 900 ° C. for 1 hour in an electric furnace, and a conductor film having a fired film thickness of 13 ⁇ m was baked on the ceramic substrate. Otherwise, the electronic component according to Example 12 was produced in the same manner as Example 11.
- Example 13 In this example, a substantially spherical Ag powder having an average particle diameter of 2.0 ⁇ m was used as the base of the metal powder. Coating with an organic metal compound is not performed. That is, using these uncoated Ag powders as they are, these materials are weighed so that the final paste concentration (weight ratio) is 87 wt% of the Ag powder and the balance is the vehicle (terpineol and ethyl cellulose), and a three-roll mill is used. Kneaded. In this way, a conductor paste according to Example 12 was prepared. Next, a conductor film was formed on the surface of the green sheet (glass ceramic substrate) using the conductor paste according to Example 13 and the green sheet according to Example 5.
- the glass sheet is formed by previously firing the green sheet in an electric furnace at 900 ° C. for 1 hour and then sintering the green sheet by the firing process based on a general screen printing method.
- a conductor paste was applied to the surface of the material to form a coating film having a predetermined film thickness.
- this conductor film was fired together with the glass ceramic substrate (post-baking). That is, the baking process for 45 minutes was performed at the temperature of 850 degreeC in the electric furnace. By this firing treatment, a conductor film having a fired film thickness of 12 ⁇ m was baked on the glass ceramic substrate.
- the electronic component according to Example 13 was manufactured in the same manner as Example 1.
- Example 14 In the same manner as in Example 13, the conductor film was baked on the glass ceramic substrate. Next, electroless Ni / Au plating was applied to the surface of the conductor film (plating thickness 0.5 ⁇ m). Next, a bonding wire was connected to a part of the plated conductor film under the same conditions as in Example 1 to produce an electronic component according to Example 14.
- Example 15 A paste containing (Si—Zn—RO-based glass containing SiO 2 , ZnO, B 2 O 3 and BaO) as an oxide glass powder was prepared.
- a conductor paste according to Example 15 was prepared in the same manner as Example 13.
- a conductor film having a fired film thickness of 11 ⁇ m was baked on a glass ceramic substrate. Otherwise, the electronic component according to Example 15 was fabricated in the same manner as Example 13.
- Example 16 A substantially spherical Ag powder having an average particle size of 0.2 ⁇ m was used. Then, the same treatment as Example 1 to obtain a Ag powder whose surface is substantially uniformly coated with zirconium alkoxide at a quantity corresponding to 0.1 parts by mass with respect to 100 parts by mass of the Ag powder in terms of ZrO 2. The materials used were weighed so that the final paste concentration (weight ratio) was 87 wt% of Zr-coated Ag powder and the balance was a vehicle (terpineol and ethyl cellulose), and kneaded using a three-roll mill. In this way, a conductor paste according to Example 16 was prepared.
- Example 16 Using the conductor paste according to Example 16, firing treatment (post-baking) was performed at 850 ° C. to 900 ° C. for 45 minutes in an electric furnace, and a conductor film having a fired film thickness of 14 ⁇ m was baked on the glass ceramic substrate. Otherwise, the electronic component according to Example 16 was manufactured in the same manner as Example 13.
- Example 17 A substantially spherical Ag powder having an average particle size of 0.4 ⁇ m was used. Then, the same treatment as Example 1 to obtain a Ag powder whose surface is substantially uniformly coated with zirconium alkoxide at a quantity corresponding to 0.01 parts by mass with respect to 100 parts by mass of the Ag powder in terms of ZrO 2. The materials used were weighed so that the final paste concentration (weight ratio) was 87 wt% of Zr-coated Ag powder and the balance was a vehicle (terpineol and ethyl cellulose), and kneaded using a three-roll mill. In this way, a conductor paste according to Example 17 was prepared.
- the conductor paste according to Example 17 was baked (simultaneously baked) at 850 ° C. to 900 ° C. for 1 hour in an electric furnace, and a conductor film having a fired film thickness of 14 ⁇ m was baked on the glass ceramic substrate.
- an electronic component according to Example 17 was produced in the same manner as Example 5.
- Example 18 An Ag powder whose surface was almost uniformly coated with zirconium alkoxide in an amount of 0.25 part by mass with respect to 100 parts by mass of Ag powder in terms of ZrO 2 was obtained. Otherwise, the electronic component according to Example 18 was fabricated in the same manner as Example 17.
- Example 19 A substantially spherical Ag powder having an average particle size of 8.0 ⁇ m was used. Then, the same treatment as Example 1 to obtain a Ag powder whose surface is substantially uniformly coated with zirconium alkoxide at a quantity corresponding to 0.05 parts by mass with respect to 100 parts by mass of the Ag powder in terms of ZrO 2. The materials used were weighed so that the final paste concentration (weight ratio) was 87 wt% of Zr-coated Ag powder and the balance was vehicle (terpineol and ethyl cellulose), and 0.5 parts by mass with respect to 100 parts by mass of Ag powder.
- Example 19 An amount of bismuth oxide (Bi 2 O 3 ) and an amount of copper oxide (Cu 2 O) of 0.5 parts by mass with respect to 100 parts by mass of Ag powder were added and kneaded using a three-roll mill. . Thereby, a conductor paste according to Example 19 was prepared. Using the conductor paste according to Example 19, a firing process (simultaneous firing) at 900 ° C. for 1 hour was performed in an electric furnace, and a conductor film having a fired film thickness of 13 ⁇ m was baked on the glass ceramic substrate. Otherwise, the electronic component according to Example 19 was produced in the same manner as Example 5.
- the average particle size of Ag powder, the coating amount of the organic metal compound (ie, zirconium alkoxide), the type and amount of the additive, the presence / absence of Ni / Au plating, the fired film thickness, the firing temperature, the inorganic group The materials and firing methods are shown in columns in Tables 1 to 5 below.
- wire bondability that is, initial tensile strength and tensile strength after pressure cooker test (PCT)
- PCT pressure cooker test
- solder heat resistance solder weather resistance
- the wire bonding property was evaluated for the electronic components according to the above examples.
- (1) Initial tensile strength measurement test As shown in FIG. 3, the bonding wire connected to the conductor film 120 on the inorganic base material (ceramic base material or glass ceramic base material) 110 of the electronic component 100 according to each of the above examples. 130 is pulled up in the direction of arrow X at a speed of 0.5 mm / sec upward in the vertical direction by a bonding tester 200 (here, model PTR-1000 manufactured by RHESCA Co., Ltd. is used) The initial tensile strength (g) when it broke was measured.
- a bonding tester 200 here, model PTR-1000 manufactured by RHESCA Co., Ltd. is used
- the initial tensile strength refers to the tensile strength of the bonding wire immediately after the bonding wire is connected to the conductor film.
- (2) Post-PCT tensile strength measurement test A pressure cooker test (PCT) was performed on the electronic components according to the above examples under conditions of a temperature of 121 ° C., a humidity of 98% RH, a pressure of 2 atm, and 60 hours. And the post-PCT tensile strength (g) was measured on the bonding wire of the electronic component which concerns on each example after PCT on the same conditions as the measurement test of said (1).
- solder heat resistance evaluation test The conductor paste according to Examples 1 to 19 was applied to the surface of a test piece 45 mm ⁇ 32 mm ⁇ 0.8 mm rectangular parallelepiped shape made of an inorganic base material according to each example with a width of 0.2 mm.
- the conductor paste was baked under the same conditions as those for manufacturing the electronic component according to each example, and the conductor film was baked on the test piece.
- coating rosin flux to the conductor film part of the test piece which concerns on each example, the said test piece was immersed in the solder (Sn / Pb 60/40 (weight ratio)) of 260 degreeC for 10 second.
- solder heat resistance was evaluated by the area ratio of the conductor film remaining on the base material (substrate) after the immersion, compared with the portion that was not “soldered” after the immersion, that is, before the immersion.
- 4 to 6 are photographs showing the states of the conductor films according to Example 4, Example 1, and Example 13 after the solder heat resistance evaluation test (photos of other examples are not shown). Those without solder breakage (that is, those in which the conductor film was not dissolved in the solder) were judged to exhibit excellent solder heat resistance, and indicated by ⁇ in the table. In addition, although solder cracks were generated, those in which approximately 90% or more of the conductor film remained were judged as exhibiting good solder heat resistance, and indicated by ⁇ in the table.
- solder temperature condition and the immersion time were set to 235 ⁇ 5 ° C. ⁇ 2 ⁇ 0.5 seconds.
- the solder weather resistance was evaluated based on the area ratio of the solder covering the surface of the conductor film after immersion. Those with no solder peeling were judged to exhibit excellent solder weather resistance, and were indicated by ⁇ in the table.
- the conductor paste of the present invention that is, the Ag metal powder has an average particle size of 0.3 to 6.0 ⁇ m, and an oxide of Zr relative to 100 parts by mass of the Ag metal powder.
- a conductor film formed from a paste containing an amount corresponding to 0.02 to 0.1 parts by mass in terms of conversion was confirmed to have excellent initial tensile strength and tensile strength after PCT, and excellent wire bonding properties (example) 1 to Example 12).
- the wire bonding property was improved by adding an appropriate amount of oxide glass powder or inorganic oxide powder to the conductor paste (for example, Example 10). And Example 11, Example 8, Example 7 and Example 9).
- the electronic component of Example 14 it was confirmed that the initial tensile strength was excellent by plating the conductor film (wire bonding portion), but the post-PCT tensile strength was poor and insufficient. It was confirmed that there was.
- solder heat resistance evaluation test it was confirmed that the conductor film formed by the wire bonding portion forming conductor paste of the present invention had good solder heat resistance as another characteristic ( Examples 1 to 12. It was confirmed that the heat resistance of the solder was particularly excellent in the examples where the additives were added (Examples 4 to 7, Example 9, Example 11 and Example 12).
- the semiconductor element or the like can be solder-mounted on the conductor film without plating the surface of the conductor film.
- solder weather resistance evaluation test it was confirmed that the conductor film formed with the wire bonding portion forming conductor paste of the present invention had good solder weather resistance as another characteristic ( Examples 1 to 12). Therefore, an electronic component in which a semiconductor element or the like is directly solder-mounted on a conductor film formed using the above-described conductor paste is considered to have a property that the semiconductor element or the like is not easily peeled off from the conductor film even when used for a long time. It is done.
- a conductive film on a substrate using the conductive film forming material (conductive paste) of the present invention an electronic component mounted on the substrate (inorganic substrate) using solder, and a wire Electronic components can be mounted with the same conductor film forming material (composition) for each electronic component mounted using bonding.
- the conductor paste of the present invention a conductor film excellent in wire bonding property, solder heat resistance and solder weather resistance can be formed. For this reason, the present invention can provide an electronic component that can withstand long-time use since the semiconductor element and the conductor film are connected with the bonding wire in a state in which sufficient connection strength is ensured. Furthermore, since the conductor paste of the present invention can be used for each of the case where an electronic component such as a semiconductor element is soldered on a substrate and the case where the electronic component is mounted using wire bonding, it can contribute to the reduction of the manufacturing process.
- Electronic parts 20 Glass ceramic substrate (inorganic substrate) 30 Conductive films 40 and 45 Wire bonding portions 50 and 55 Bonding wires 60 and 65 Semiconductor elements 70 and 75 Bonding pad 100 Electronic component 110 Inorganic substrate 120 Conductive film 130 Bonding wire 200 Bonding tester
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Abstract
Description
なお、本出願は2010年5月11日に出願された日本国特許出願2010-109596号に基づく優先権を主張しており、その出願の全内容は本明細書中に参照として組み入れられている。
そこで、接続に必要な接続強度(ワイヤボンディング性)を満足するべく、従来はAgから構成された導体膜の表面に無電解Ni/Au又は無電解Ni/Pd/Au等を用いた湿式めっき処理を施す手法が採用されている。
そこで、本発明は、上述した従来の課題を解決すべく創出されたものであり、その目的は、ワイヤボンディング性に優れた湿式めっきレスの導体膜を基板の表面に備える電子部品ならびに該電子部品の製造方法を提供することである。また、そのような電子部品を構築するために用いられるワイヤボンディング性に優れた湿式めっきレスの導体膜を形成する材料の提供を他の目的の一つとする。また、基板上に半田付けによって搭載する電子部品とワイヤボンディングによって搭載する電子部品とのそれぞれに対して、同一の導体膜形成用材料での搭載が可能となる導体膜形成用材料の提供を他の目的の一つとする。
かかる構成によると、導体膜の焼結性が高まって、導体膜とボンディングワイヤとのワイヤボンディング部における機械的接続強度(即ちワイヤボンディング性)をより向上させることができる。なお、かかる構成の導体膜は、半田耐熱性に優れるためワイヤボンディング部以外の導体膜、例えば、半導体チップ等を搭載するための導体膜を形成した場合、半導体チップ等を基材の上に実装する(取り付ける)際の半田くわれの発生を効果的に防止することができる。
特に、上記添加物として無機酸化物を含んでおり、該無機酸化物は酸化ビスマスと酸化銅との混合物であって、該混合物の添加量は、上記Ag系金属100質量部に対して0.5~5質量部に相当する量であることが好ましい。
或いは、上記添加物として酸化物ガラスを含んでおり、該ガラスの添加量は、上記Ag系金属100質量部に対して0.05~0.5質量部に相当する量であることが好ましい。
或いは、ここで開示される電子部品の好適な一態様では、上記無機基材は、ガラス成分を主成分とする非晶質セラミックスから成る非晶質セラミック基材であり、上記導体膜のうちの少なくとも上記ワイヤボンディング部を形成する部分は、上記添加物として酸化物ガラスを含んでいる。ここで、主成分とは全体の50質量%を上回る量の成分をいい、典型的には70質量%以上のものをいう。
かかる金属材料から構成されるボンディングワイヤは、例えば半導体素子と導体膜とを電気的および機械的に接続するのに好適に用いることができる。
かかる構成の導体ペーストによると、ワイヤボンディング性をより向上させた導体膜を形成することができる。なお、かかる構成の導体ペーストを用いて形成された導体膜は、半田耐熱性に優れるためワイヤボンディング部以外の導体膜、例えば、半導体チップ等を搭載するための導体膜を形成した場合、半導体チップ等を基材の上に実装する(取り付ける)際の半田くわれの発生を効果的に防止することができる。
或いは、上記添加物として酸化物ガラス粉末を含んでおり、該ガラス粉末の添加量は、上記Ag系金属粉末100質量部に対して0.05~0.5質量部に相当する量であることが好ましい。
ここで、上記有機系金属化合物若しくは上記金属酸化物のコーティング量は、上記Ag系金属粉末100質量部に対して金属酸化物換算で0.02~0.1質量部に相当する量である;を有するワイヤボンディング部形成用導体ペーストを用意すること、(2)上記導体ペーストを上記無機基材の表面に塗布して、該無機基材の表面に導体膜を形成すること、及び(3)上記形成した導体膜の一部に上記ボンディングワイヤをボンディングすること、を包含する。
或いは、上記添加物として酸化物ガラス粉末を含んでおり、該ガラス粉末の添加量は、上記Ag系金属粉末100質量部に対して0.05~0.5質量部に相当する量であることが好ましい。
或いは、ここで開示される電子部品の製造方法の好適な一態様では、上記無機基材がガラス成分を主成分とする非晶質セラミック基材であって、上記導体ペーストは、上記添加物として酸化物ガラス粉末を含んでいることを特徴とする。
本発明に係るワイヤボンディング部形成用導体ペースト(以下、単に「導体ペースト」という。)は、Ag系金属粉末を主成分とすることで特徴付けられるワイヤボンディング部形成用ペーストであって、上記目的を達成し得る限りにおいて他の副成分の内容や組成に特に制限はない。
Ag系金属粉末は、Ag若しくはAg主体の合金(例えばAg-Au合金、Ag-Pd合金)から実質的に構成されている微粒子群である。かかるAg系金属粉末としては、導電性付与の観点から、Ag単体または比抵抗値が概ね1.8~5.0×10-6Ω・cm(好ましくは1.9~3.0×10-6Ω・cm、例えば2.2×10-6Ω・cm)の合金から成るものが適当である。また、特に限定するものではないが、平均粒径が0.3~6.0μmのAg系金属粉末が好ましい。また、そのような比較的微小な平均粒径を有し且つ粒径10μm以上(特に好ましくは粒径8μm以上)の粒子を実質的に含まないような粒度分布の比較的狭いAg系金属粉末が特に好ましい。
なお、Ag系金属粉末自体は、従来公知の製造方法によって製造されたものでよく、特別な製造手段を要求するものではない。例えば、周知の還元析出法、気相反応法、ガス還元法等によって製造されたAg系金属粉末を使用することができる。
Ag系金属粉末のコーティングに使用する有機系金属化合物としては、最終的(焼成後)にAg系金属粉末の表面に本発明の目的の実現に適う金属(金属酸化物又はその還元物を含む)の被膜(即ち当該表面を被覆する付着物)を形成し得るものであれば特に制限はない。好適な構成金属元素として、Al、もしくはZr、もしくはTi、もしくはY、もしくはCa、もしくはMg、もしくはZn等が挙げられる。これらを構成元素とする有機酸金属塩、金属アルコキシド又はキレート化合物が好適に用いられる。
例えば、好適な金属アルコキシドとしては、ジルコニウムエトキシド、ジルコニウムブトキシド等のジルコニウムアルコキシド、アルミニウムエトキシド(Al(OC2H5)3)、アルミニウムt-ブトキシド(Al(OC(CH3)3)3)、アセトアルコキシアルミニウムジイソプロピレート、アセトアルコキシアルミニウムエチルアセトアセテート、アセトアルコキシアルミニウムアセチルアセトネート等のアルミニウムアルコキシド、テトラプロポキシチタン(Ti(OC3H7)4)等のチタン(IV)アルコキシドの他、Zn、Mg、Ca等を中心金属原子(イオン)とする種々の多核アルコラト錯体が挙げられる。また、好適なキレート化合物としては、Zn、Mg、Ca等を中心金属原子(イオン)とするエチレンジアミン(en)錯体、エチレンジアミンテトラアセタト(edta)錯体等が挙げられる。或いは、Ti、Zn、Mg等の金属(イオン)とキレートを形成した所謂キレート樹脂も、本発明に係る有機系金属化合物(キレート化合物)として好適である。
本発明の導体ペーストの副成分として、上記金属粉末を分散させておく有機媒質(ビヒクル)が挙げられる。本発明の実施にあたっては、かかる有機ビヒクルは金属粉末を分散させておくものであればよく、従来の導体ペーストに用いられているものを特に制限なく使用することができる。例えば、エチルセルロース等のセルロース系高分子、エチレングリコール及びジエチレングリコール誘導体、トルエン、キシレン、ミネラルスピリット、ブチルカルビトール、ターピネオール等の高沸点有機溶媒が挙げられる。
これら金属酸化物粉末を副成分として添加する場合には、ペーストの充填率や分散性を適切化するという観点から、平均粒径が5μm以下(典型的には1~5μm、特に好ましくは1μm以下)の粉末が好ましい。また、比表面積については、少なくとも0.5m2/gである粉体が好ましく、1.0m2/g以上(典型的には1.0~2.0m2/g、特に好ましくは2.0~100m2/g)である粉体が特に好ましい。
有機バインダとしては、例えば、アクリル樹脂、エポキシ樹脂、フェノール樹脂、アルキド樹脂、セルロース系高分子、ポリビニルアルコール等をベースとするものが挙げられる。本発明の導体ペーストに良好な粘性及び塗膜(無機基材に対する付着膜)形成能を付与し得るものが好適である。また、本発明の導体ペーストに光硬化性(光性)を付与したい場合には、種々の光重合性化合物及び光重合開始剤を適宜添加してもよい。上記の他にも本発明に係る導体ペーストには、必要に応じて界面活性剤、消泡剤、可塑剤、増粘剤、酸化防止剤、分散剤、重合禁止剤等を適宜添加することができる。これら添加剤は、従来の導体ペーストの調製に用いられ得るものであればよく、詳細な説明は省略する。
セラミック基材としては、主成分がアルミナ、ジルコニア等のセラミック材料から構成されるもの、若しくは一般式xBaO・yNd2O3・zTiO2(6≦x≦23、13≦y≦30、64≦z≦68、x+y+z=100)、該主成分に対して副成分としてCu酸化物をCuO換算で0.1~3.0質量%、Zn酸化物をZnO換算で0.1~4.0質量%、B酸化物をB2O3換算で0.1~3.0質量%の範囲で含有する誘電体磁器組成物が挙げられる。
グリーンシートは、典型的には、ガラス成分とフィラー(例えばアルミナ)とバインダとを有機溶剤とともに混合してスラリー状の誘電体ペーストを調製し、これを例えばポリエチレンテレフタレート(PET)シート等の支持体上にドクターブレード法等によって成膜することにより形成される。バインダは、従来公知のものを特に制限なく使用することができる。例えば、エチルセルロース、ポリビニルブチラール等が挙げられる。また、有機溶剤も従来公知のものを特に制限なく使用することができる。例えば、ターピネオール、ブチルカルビトール、アセトン及びトルエン等が挙げられる。
まず、Ag系金属粉末の表面への有機系金属化合物又はその金属酸化物のコーティング方法、すなわち所定の有機系金属化合物でコーティングされた金属粉末の製造方法について説明する。
本発明の実施に用いられる金属粉末は、その主体たるAg系金属粉末の表面に満遍なくほぼ均等に有機系金属化合物又はその金属酸化物がコーティングされるのが好ましいが、そのコーティング方法に特に制限はない。例えば、従来知られている金属粒子への有機物コーティング方法をそのまま適用することができる。一例を挙げると、先ず、トルエン、キシレン、各種アルコール等の適当な有機溶剤に所望の有機系金属化合物を溶解若しくは分散する。次いで、得られた溶液若しくは分散液(ゾル)にAg系金属粉末を添加し、分散・懸濁する。この懸濁液を所定時間静置又は撹拌することによって、当該懸濁液中のAg系金属粉末の表面を目的の有機系金属化合物でコーティングすることができる。このとき、特に限定するものではないが、好ましくは有機系金属化合物又はその金属酸化物のコーティング量が酸化物換算でAg系金属粉末100質量部に対して0.02~0.1質量部(例えば0.025~0.1質量部)に相当する量となるように所望する有機系金属化合物若しくは金属酸化物をAg系金属粉末にコーティングする。かかるコーティング量が酸化物換算でAg系金属粉末100質量部に対して0.02質量部に相当する量よりも少なすぎる場合には、コーティングの効果が希薄であり、本発明に関する上記目的を達成し難い。他方、かかるコーティング量が酸化物換算でAg系金属粉末100質量部に対して0.1質量部に相当する量よりも過剰に多い場合には、Ag系金属粉末本来の電気的特性等の諸機能が損なわれる虞があるため好ましくない。
ペースト調製に用いられる有機ビヒクルの添加量は、ペースト全体のほぼ1~40質量%となる量が適当であり、1~20質量%となる量が特に好ましい。
また、添加物として上述の無機酸化物粉末を加える場合には、Ag系金属粉末100質量部に対して0.5~5質量部程度の使用が好ましい。より好ましくは0.5~3質量部程度である。さらに好ましくは1~2質量部程度である。かかる低率の添加量によると、本発明に係る導体ペーストの良好な導電率や半田濡れ性を実質的に損なうことなく、本発明のペーストから得られる焼成物(導体膜)の無機基材に対する接着強度の向上及び焼成収縮の抑制、さらにはワイヤボンディング性及び半田耐熱性の向上を実現することができる。なお、特に限定するものではないが、無機基材としてセラミック基材を用いる場合には、導体ペーストに無機酸化物粉末を加えるのが好ましい。
他方、添加物として上述のガラス粉末を加える場合には、Ag系金属粉末100質量部に対して0.05~0.5質量部程度の使用が好ましい。より好ましくは0.1~0.3質量部程度である。さらに好ましくは0.1~0.2質量部程度である。かかる低率の添加量によると、本発明に係る導体ペーストの良好な導電率や半田濡れ性を実質的に損なうことなく、本発明のペーストから得られる焼成物(導体膜)の無機基材に対する接着強度の向上、さらにはワイヤボンディング性及び半田耐熱性の向上を実現することができる。なお、特に限定するものではないが、無機基材としてガラスセラミック基材(グリーンシート)を用いる場合には、導体ペーストにガラス粉末を加えるのが好ましい。
特に限定するものではないが、Ag系金属粉末として平均粒径が3.0~6.0μmである金属粉末を使用し、且つ添加物として無機酸化物粉末及び/又は酸化物ガラス粉末を含む導体ペーストを好ましい用いることができる。
なお、特に限定するものではないが、無機基材としてセラミック基材を用いる場合には、予めセラミック基材の焼成処理を行い、焼成後のセラミック基材上に導体ペーストを塗布して、該導体ペーストを焼成する処理(後焼き)を行うことが好ましい。これにより、セラミック基材上に目的の導体膜が形成される。
一方、無機基材としてガラスセラミック基材を用いる場合には、グリーンシート上に導体ペーストを塗布して、グリーンシートと導体ペーストとを焼成処理(同時焼成)することが好ましい。これにより、グリーンシートが焼成されて形成されたガラスセラミック基材上に目的の導体膜が形成される。
本発明の導体ペーストにより形成された導体膜は、従来のように導体膜表面をめっき処理することなく、半導体素子等と導体膜とをボンディングワイヤによって直接接続することができる。さらに導体膜とボンディングワイヤの接続部分(ワイヤボンディング部)において十分な接続強度(ワイヤボンディング性)を備えている。
ボンディングワイヤは、ワイヤボンディングする際に用いられる従来と同様のものを使用することができる。例えば、金、アルミニウム及び銅のうちのいずれかの金属元素を主構成要素とする金属製のワイヤが挙げられる。
なお、本発明に係る導体ペーストにより形成された導体膜は、半田耐熱性および半田耐候性に優れていることから、種々の半導体素子等を導体膜上に半田によって搭載する場合に好適に用いることができる。
セラミック基材20の表面に所定パターンの導体膜30(典型的には配線、電極)が形成されており、該導体膜30の一部に半導体素子60,65がリフロー方式によりそれぞれ半田実装されている。そして、半導体素子60に形成された複数のボンディングパッド(典型的にはアルミ電極)70と、導体膜30とが、ボンディングワイヤ50によって機械的及び電気的にそれぞれ接続されている。同様に、半導体素子65のボンディングパッド75と導体膜30とがボンディングワイヤ55によって接続されている。本発明に係る電子部品では、導体膜30とボンディングワイヤ50,55とが接続した部分、即ちワイヤボンディング部40,45において、十分な機械的接続強度(ワイヤボンディング性)での接続が実現されている。
本例では、金属粉末のベースとして、一般的な湿式法により調製された平均粒径が0.7μmの略球状のAg粉末を使用した。一方、該Ag粉末をコーティングする材料として、ジルコニウムアルコキシド(ここではジルコニウムブトキシド)を用いた。而して、適当な有機溶媒(ここではメタノール)に上記金属アルコキシドを添加し、濃度5~100g/lのコーティング用溶液を調製した。次いで、かかる溶液中に上記Ag粉末を適当量懸濁させ、適宜撹拌しつつ1~3時間懸濁状態を維持した。その後、Ag粉末を回収し、60~110℃で通風乾燥した。
以上の処理によって、酸化ジルコニウム(ZrO2)換算でAg粉末100質量部に対して0.05質量部となる量の上記ジルコニウムアルコキシドによって表面がほぼ均等にコーディングされたAg粉末(以下「ZrコーティングAg粉末」)という。)を得た。
次に、上記得られたZrコーティングAg粉末を使用して導体ペーストを調製した。すなわち、最終的なペースト濃度(重量比)がZrコーティングAg粉末87wt%および残部がビヒクル(ここではターピネオールとエチルセルロース)となるように使用材料を秤量し、三本ロールミルを用いて混錬した。これにより、例1に係る導体ペーストを調製した。
<ワイヤボンディング条件>
ボンディングワイヤ:99.99%Au、直径25μm(GMH2;田中電子工業製)
キャピラリー:1551-W3-BNIA(GAISER製)
超音波出力時間(1st,2nd):25ms,30ms
超音波出力(1st,2nd):65bit,75bit
ボンド荷重(1st,2nd):55g,70g
ワイヤボンディング温度:100℃
このワイヤボンディングにより、セラミック基材に焼き付けられた導体膜の一部にボンディングされたボンディングワイヤを備える例1に係る電子部品を作製した。
電気炉中で850℃、45分間の焼成処理(後焼き)を行った他は例1と同様にして、例2に係る電子部品を作製した。
電気炉中で900℃、45分間の焼成処理(後焼き)を行い、焼成膜厚み12μmの導体膜をセラミック基材上に焼き付けた。その他の点については例1と同様にして、例3に係る電子部品を作製した。
平均粒径が2.0μmの略球状のAg粉末を使用した。そして、例1と同様の処理を行い、ZrO2換算でAg粉末100質量部に対して0.1質量部となる量のジルコニウムアルコキシドによって表面がほぼ均等にコーティングされたAg粉末を得た。
最終的なペースト濃度(重量比)がZrコーティングAg粉末87wt%および残部がビヒクル(ここではターピネオールとエチルセルロース)となるように使用材料を秤量し、さらにAg粉末100質量部に対して0.5質量部となる量の酸化ビスマス(Bi2O3)と、Ag粉末100質量部に対して0.5質量部となる量の酸化銅(Cu2O)とを加え、三本ロールミルを用いて混錬した。これにより、例4に係る導体ペーストを調製した。
例4に係る導体ペーストを用いて、電気炉中で850℃、45分間の焼成処理(後焼き)を行い、焼成膜厚み13μmの導体膜をセラミック基材上に焼き付けた。その他の点については例1と同様にして、例4に係る電子部品を作製した。
平均粒径が2.5μmの略球状のAg粉末を使用した。そして、例1と同様の処理を行い、ZrO2換算でAg粉末100質量部に対して0.05質量部となる量のジルコニウムアルコキシドによって表面がほぼ均等にコーティングされたAg粉末を得た。
最終的なペースト濃度(重量比)がZrコーティングAg粉末87wt%おび残部がビヒクル(ここではターピネオールとエチルセルロース)となるように使用材料を秤量し、さらにAg粉末100質量部に対して0.1質量部となる量の酸化物ガラス粉末(SiO2とZnOとB2O3とBaOとを含むSi-Zn-RO系ガラス)を加え、三本ロールミルを用いて混錬した。これにより、例5に係る導体ペーストを調製した。
次に、この導体膜をグリーンシートごと焼成した(同時焼成)。すなわち、電気炉中で900℃、1時間の焼成処理を行った。この焼成処理によって、グリーンシートが焼結されてガラスセラミック基材が形成され、導体膜を該ガラスセラミック基材上に焼き付けた。このときの焼成膜厚みは13μmであった。次に、該ガラスセラミック基材に形成された導体膜の一部に例1と同様の条件でワイヤボンディングを行い、例5に係る電子部品を作製した。
ZrO2換算でAg粉末100質量部に対して0.025質量部となる量のジルコニウムアルコキシドによって表面がほぼ均等にコーティングされたAg粉末を用いた。その他の点については例5と同様にして、例6に係る電子部品を作製した。
平均粒径が0.4μmの略球状のAg粉末を使用した。そして、例1と同様の処理を行い、ZrO2換算でAg粉末100質量部に対して0.1質量部となる量のジルコニウムアルコキシドによって表面がほぼ均等にコーティングされたAg粉末を得た。
最終的なペースト濃度(重量比)がZrコーティングAg粉末87wt%および残部がビヒクル(ここではターピネオールとエチルセルロース)となるように使用材料を秤量し、さらにAg粉末100質量部に対して0.2質量部となる量の酸化物ガラス粉末(SiO2とZnOとB2O3とBaOとを含むSi-Zn-RO系ガラス)を加え、三本ロールミルを用いて混錬した。これにより、例7に係る導体ペーストを調製した。
例7に係る導体ペーストを用いて、電気炉中で850℃、1時間の焼成処理(同時焼成)を行い、焼成膜厚み15μmの導体膜をガラスセラミック基材上に焼き付けた。その他の点については例3と同様にして、例7に係る電子部品を作製した。
ペースト調製において酸化物ガラス粉末を添加しなかった点以外は、例7と同様にして、例8に係る導体ペーストを調製した。
例8に係る導体ペーストを用いて、電気炉中で850℃、45分間の焼成処理(後焼き)を行い、焼成膜厚み15μmの導体膜をセラミック基材上に焼き付けた。その他の点については例1と同様にして、例8に係る電子部品を作製した。
無機酸化物として酸化ビスマス(Bi2O3)と酸化銅(Cu2O)を含有するペーストを調製した。Ag粉末100質量部に対して0.5質量部となる量の酸化ビスマスと、Ag粉末100質量部に対して0.5質量部となる量の酸化銅を用いた。その他の点については、例8と同様にして、例9に係る導体ペーストを調製した。
例9に係る導体ペーストを用いた。その他の点については例8と同様にして、例9に係る電子部品を作製した。
平均粒径が3.5μmの略球状のAg粉末を使用した。そして、例1と同様の処理を行い、ZrO2換算でAg粉末100質量部に対して0.1質量部となる量のジルコニウムアルコキシドによって表面がほぼ均等にコーティングされたAg粉末を得た。
最終的なペースト濃度(重量比)がZrコーティングAg粉末87wt%おび残部がビヒクル(ターピネオールとエチルセルロース)となるように使用材料を秤量し、三本ロールミルを用いて混錬した。これにより、例10に係る導体ペーストを調製した。
次に、例10に係る導体ペーストおよび例1と同様のセラミック基材を用いて、該セラミック基材の表面に導体膜を形成した。すなわち、一般的なスクリーン印刷法に基づいてセラミック基材の表面に導体ペーストを塗布し、所定の膜厚の塗膜を形成した。続いて、遠赤外線乾燥機を用いて100℃で15分間の乾燥処理を施した。
次に、この導体膜をセラミック基材ごと焼成した(同時焼成)。すなわち、電気炉中で850℃~900℃、1時間の焼成処理を行った。この焼成処理によって、焼成膜厚み14μmの導体膜をセラミック基材上に焼き付けた。その他の点については例1と同様にして、例10に係る電子部品を作製した。
無機酸化物として酸化ビスマス(Bi2O3)と酸化銅(Cu2O)を含有するペーストを調製した。Ag粉末100質量部に対して0.5質量部となる量の酸化ビスマスと、Ag粉末100質量部に対して0.5質量部となる量の酸化銅とを使用(添加)した。その他の点については、例10と同様にして、例11に係る電子部品を作製した。
平均粒径が6.0μmの略球状のAg粉末を使用した。そして、例1と同様の処理を行い、ZrO2換算でAg粉末100質量部に対して0.05質量部となる量のジルコニウムアルコキシドによって表面がほぼ均等にコーティングされたAg粉末を得た。その他の点については、例11と同様にして、例12に係る導体ペーストを調製した。
例12に係る導体ペーストを用いて、電気炉中で900℃、1時間の焼成処理(同時焼成)を行い、焼成膜厚み13μmの導体膜をセラミック基材上に焼き付けた。その他の点については例11と同様にして、例12に係る電子部品を作製した。
本例では、金属粉末のベースとして、平均粒径が2.0μmの略球状のAg粉末を使用した。有機系金属化合物によるコーティングは行っていない。すなわち、かかる非コーティングAg粉末をそのまま用いて最終的なペースト濃度(重量比)が当該Ag粉末87wt%および残部がビヒクル(ターピネオールとエチルセルロース)となるようにこれら材料を秤量し、三本ロールミルを用いて混錬した。これにより、例12に係る導体ペーストを調製した。
次に、例13に係る導体ペースト及び例5に係るグリーンシートを用いて、グリーンシート(ガラスセラミック基材)の表面に導体膜を形成した。すなわち、予め上記グリーンシートを電気炉中で900℃、1時間の焼成処理を行った後、一般的なスクリーン印刷法に基づいて上記焼成処理によってグリーンシートが焼結されて形成されたガラスセラミック基材の表面に導体ペーストを塗布し、所定の膜厚の塗膜を形成した。
次に、この導体膜をガラスセラミック基材ごと焼成した(後焼き)。すなわち、電気炉中で850℃の温度で45分間の焼成処理を行った。この焼成処理によって、焼成膜厚み12μmの導体膜をガラスセラミック基材上に焼き付けた。その他の点については例1と同様にして、例13に係る電子部品を作製した。
例13と同様にして、導体膜をガラスセラミック基材上に焼き付けた。次に、該導体膜の表面に無電解Ni/Auめっきを施した(めっき厚さ0.5μm)。次に、めっきが施された導体膜の一部にボンディングワイヤを例1と同様の条件で接続し、例14に係る電子部品を作製した。
酸化物ガラス粉末として(SiO2とZnOとB2O3とBaOとを含むSi-Zn-RO系ガラス)を含有するペーストを調製した。Ag粉末100質量部に対して2.0質量部となる量の上記酸化物ガラス粉末を使用(添加)した。その他の点については、例13と同様にして、例15に係る導体ペーストを調製した。
例15に係る導体ペーストを用いて、焼成膜厚み11μmの導体膜をガラスセラミック基材上に焼き付けた。その他の点については例13と同様にして、例15に係る電子部品を作製した。
平均粒径が0.2μmの略球状のAg粉末を使用した。そして、例1と同様の処理を行い、ZrO2換算でAg粉末100質量部に対して0.1質量部となる量のジルコニウムアルコキシドによって表面がほぼ均等にコーティングされたAg粉末を得た。
最終的なペースト濃度(重量比)がZrコーティングAg粉末87wt%および残部がビヒクル(ターピネオールとエチルセルロース)となるように使用材料を秤量し、三本ロールミルを用いて混錬した。これにより、例16に係る導体ペーストを調製した。
例16に係る導体ペーストを用いて、電気炉中で850℃~900℃、45分間の焼成処理(後焼き)を行い、焼成膜厚み14μmの導体膜をガラスセラミック基材上に焼き付けた。その他の点については例13と同様にして、例16に係る電子部品を作製した。
平均粒径が0.4μmの略球状のAg粉末を使用した。そして、例1と同様の処理を行い、ZrO2換算でAg粉末100質量部に対して0.01質量部となる量のジルコニウムアルコキシドによって表面がほぼ均等にコーティングされたAg粉末を得た。
最終的なペースト濃度(重量比)がZrコーティングAg粉末87wt%および残部がビヒクル(ターピネオールとエチルセルロース)となるように使用材料を秤量し、三本ロールミルを用いて混錬した。これにより、例17に係る導体ペーストを調製した。
例17に係る導体ペーストを用いて、電気炉中で850℃~900℃、1時間の焼成処理(同時焼成)を行い、焼成膜厚み14μmの導体膜をガラスセラミック基材上に焼き付けた。その他の点については例5と同様にして、例17に係る電子部品を作製した。
ZrO2換算でAg粉末100質量部に対して0.25質量部となる量のジルコニウムアルコキシドによって表面がほぼ均等にコーティングされたAg粉末を得た。その他の点については例17と同様にして、例18に係る電子部品を作製した。
平均粒径が8.0μmの略球状のAg粉末を使用した。そして、例1と同様の処理を行い、ZrO2換算でAg粉末100質量部に対して0.05質量部となる量のジルコニウムアルコキシドによって表面がほぼ均等にコーティングされたAg粉末を得た。
最終的なペースト濃度(重量比)がZrコーティングAg粉末87wt%および残部がビヒクル(ターピネオールとエチルセルロース)となるように使用材料を秤量し、さらにAg粉末100質量部に対して0.5質量部となる量の酸化ビスマス(Bi2O3)と、Ag粉末100質量部に対して0.5質量部となる量の酸化銅(Cu2O)とを加え、三本ロールミルを用いて混錬した。これにより、例19に係る導体ペーストを調製した。
例19に係る導体ペーストを用いて、電気炉中で900℃、1時間の焼成処理(同時焼成)を行い、焼成膜厚み13μmの導体膜をガラスセラミック基材上に焼き付けた。その他の点については例5と同様にして、例19に係る電子部品を作製した。
なお、上述の例におけるAg粉末平均粒径、有機系金属化合物(即ちジルコニウムアルコキシド)のコーティング量、添加物の種類及びその添加量、Ni/Auめっきの有無、焼成膜厚み、焼成温度、無機基材及び焼成方法を、以下の表1~5に欄を設けて示している。
上記各例に係る電子部品につき、ワイヤボンディング性を評価した。
(1)初期引張強度測定試験
図3に示すように、上記各例に係る電子部品100の無機基材(セラミック基材或いはガラスセラミック基材)110上の導体膜120に接続されているボンディングワイヤ130を、ボンディングテスタ200(ここでは株式会社RHESCA製の型式PTR-1000を用いた。)にて、鉛直方向上側に0.5mm/secの速度で矢印Xの方向に引っ張り上げて、ボンディングワイヤが破断したときの初期引張強度(g)を測定した。ここで初期引張強度とは、導体膜にボンディングワイヤを接続した直後のボンディングワイヤの引張強度をいう。
(2)PCT後引張強度測定試験
上記各例に係る電子部品に対して、温度121℃、湿度98%RH、圧力2atm、60時間の条件下でそれぞれプレッシャークッカーテスト(PCT)を行った。そして、PCT後の各例に係る電子部品のボンディングワイヤに対して、上記(1)の測定試験と同じ条件下でPCT後引張強度(g)を測定した。
初期引張強度及びPCT後引張強度のいずれもが6(g)以上の場合には、ワイヤボンディング性が優れていると判断して表中において◎で示した。また、初期引張強度及びPCT後引張強度のいずれか一方が6(g)以上の場合には、ワイヤボンディング性があると判断して表中において○で示した。他方、初期引張強度及びPCT後引張強度のいずれもが6(g)より小さい場合にはワイヤボンディング性が劣ると判断して表中において×で示した。
上記例1~例19に係る導体ペーストを、それぞれ各例に係る無機基材からなるテストピース45mm×32mm×0.8mmの直方体形状)の表面に、幅0.2mmで導体ペーストを塗布して、各例に係る電子部品を製造するときと同様の条件で導体ペーストの焼成処理を行い、導体膜をテストピース上に焼き付けた。そして、各例に係るテストピースの導体膜部分にロジンフラックスを塗布した後、当該テストピースを260℃の溶融状態の半田(Sn/Pb=60/40(重量比))に10秒間浸漬した。
而して、浸漬後に「半田くわれ」されなかった部分、即ち浸漬前と比較して浸漬後に基材(基板)上に残存している導体膜の面積比率で半田耐熱性を評価した。図4~図6は、それぞれ、例4、例1、例13に係る導体膜の上記半田耐熱性評価試験後の状態を示す写真である(他の例についての写真は掲示していない)。半田くわれがないもの(即ち、導体膜が半田中に溶解していないもの)は優れた半田耐熱性を示すものと判断し、表中において◎で示した。また、半田くわれが発生しているが、導体膜の略90%以上が残存しているものは良好な半田耐熱性を示すものと判断し、表中において○で示した。他方、導体膜の残存している部分が浸漬前の90未満のものは半田耐熱性が比較的劣っているものと判断し、表中において×で示した。なお、上記試験後の他の例に係るテストピースにおいて、図4と同様なものは◎とし、図5と同様なものは○とし、図6と同様なものは×として表中に示した。
上記例1~例19に係る導体ペーストを、それぞれ各例に係る無機基材からなるテストピース45mm×32mm×0.8mmの直方体形状)の表面に、幅0.2mmで導体ペーストを塗布して、各例に係る電子部品を製造するときと同様の条件で導体ペーストの焼成処理を行い、導体膜をテストピース上に焼き付けた。そして、各例に係るテストピースに対して、温度121℃、湿度98%RH、圧力2atm、60時間の条件下でそれぞれプレッシャークッカーテスト(PCT)を行った。そして、上記各例に係るテストピースに形成されたそれぞれの導体膜について、25%ロジンフラックスに浸漬させて導体膜形成部分にロジンフラックスを塗布した後、共晶半田(Sn/Pb=60/40(重量比))に所定時間浸漬させた。ここでは、半田温度条件及び浸漬時間を235±5℃×2±0.5秒とした。
而して、浸漬後に導体膜表面を覆っている半田の面積比率で半田耐候性を評価した。半田の剥れがないものは優れた半田耐候性を示すものと判断し、表中において◎で示した。また、半田の一部は剥れているが、導体膜の略95%以上が半田で覆われているものは良好な半田耐候性を示すものと判断し、表中において○で示した。他方、導体膜の90%未満しか半田に覆われていないものは半田耐候性が比較的劣っているものと判断し、表中において×で示した。
また、半田耐候性評価試験から明らかなように、本発明のワイヤボンディング部形成用導体ペーストにより形成された導体膜は、他の特性として良好な半田耐候性を備えていることが確認できた(例1~例12)。従って、上記導体ペーストを用いて形成された導体膜に半導体素子等を直接半田実装した電子部品は、長期間の使用に対しても半導体素子等が導体膜から剥がれ落ちにくいという性質をもつと考えられる。
このように、本発明の導体膜形成用材料(導体ペースト)を用いて導体膜を基板上に形成することによって、基板(無機基材)上に半田付けを用いて搭載する電子部品と、ワイヤボンディングを用いて搭載する電子部品とのそれぞれに対して、同一の導体膜形成用材料(組成物)での電子部品の搭載が可能となる。
20 ガラスセラミック基材(無機基材)
30 導体膜
40,45 ワイヤボンディング部
50,55 ボンディングワイヤ
60,65 半導体素子
70,75 ボンディングパッド
100 電子部品
110 無機基材
120 導体膜
130 ボンディングワイヤ
200 ボンディングテスタ
Claims (19)
- 無機基材と、該基材の表面に形成された導体膜と、該導体膜の一部にボンディングされたボンディングワイヤとを備える、少なくとも一部にワイヤボンディング部が形成された電子部品であって、
前記導体膜のうちの少なくとも前記ワイヤボンディング部を形成する部分は、Ag又はAg主体の合金から成るAg系金属と、該Ag系金属をコーティングするAl,Zr,Ti,Y,Ca,Mg及びZnから成る群から選択されるいずれかを構成要素とする金属酸化物とを含み、
前記金属酸化物のコーティング量は、前記Ag系金属100質量部に対して0.02~0.1質量部に相当する量である、ワイヤボンディング部付き電子部品。 - 前記導体膜のうちの少なくとも前記ワイヤボンディング部を形成する部分は、添加物として無機酸化物及び/又は酸化物ガラスをさらに含んでいる、請求項1に記載の電子部品。
- 前記無機基材は、結晶質セラミック基材であり、
前記導体膜のうちの少なくとも前記ワイヤボンディング部を形成する部分は、前記添加物として無機酸化物を含んでいる、請求項2に記載の電子部品。 - 前記無機基材は、ガラス成分を主成分とする非晶質セラミック基材であり、
前記導体膜のうちの少なくとも前記ワイヤボンディング部を形成する部分は、前記添加物として酸化物ガラスを含んでいる、請求項2に記載の電子部品。 - 前記無機酸化物は、酸化ビスマスと酸化銅との混合物であって、該混合物の添加量は、前記Ag系金属100質量部に対して0.5~5質量部に相当する量である、請求項3に記載の電子部品。
- 前記酸化物ガラスの添加量は、前記Ag系金属100質量部に対して0.05~0.5質量部に相当する量である、請求項4に記載の電子部品。
- 前記ボンディングワイヤは、金、アルミニウム及び銅のうちのいずれかの金属元素を主構成要素とする金属製である請求項1から6のいずれか一項に記載の電子部品。
- 無機基材と、該基材の表面に形成された導体膜と、該導体膜の一部にボンディングされたボンディングワイヤとを備える、少なくとも一部にワイヤボンディング部が形成された電子部品における少なくともワイヤボンディング部を有する導体膜を形成する用途に用いるための導体ペーストであって、
前記導体ペーストは、Ag又はAg主体の合金から成る平均粒径が0.3~6.0μmのAg系金属粉末と、該Ag系金属粉末の表面をコーティングするAl,Zr,Ti,Y,Ca,Mg及びZnから成る群から選択されるいずれかを構成要素とする有機系金属化合物若しくは金属酸化物とを含んでおり、
前記有機系金属化合物若しくは前記金属酸化物のコーティング量は、前記Ag系金属粉末100質量部に対して金属酸化物換算で0.02~0.1質量部に相当する量である、ワイヤボンディング部形成用導体ペースト。 - 添加物として無機酸化物粉末及び/又は酸化物ガラス粉末をさらに含んでいる、請求項8に記載の導体ペースト。
- 前記Ag系金属粉末の平均粒径が3.0~6.0μmのときは、添加物として無機酸化物粉末及び/又は酸化物ガラス粉末をさらに含んでいる、請求項9に記載の導体ペースト。
- 前記無機酸化物粉末は酸化ビスマスと酸化銅との混合物であって、該混合物の添加量は、前記Ag系金属粉末100質量部に対して0.5~5質量部に相当する量である、請求項9または10に記載の導体ペースト。
- 前記酸化物ガラス粉末の添加量は、前記Ag系金属粉末100質量部に対して0.05~0.5質量部に相当する量である、請求項9または10に記載の導体ペースト。
- 無機基材と、該基材の表面に形成された導体膜と、該導体膜の一部にボンディングされたボンディングワイヤとを備える、少なくとも一部にワイヤボンディング部が形成された電子部品を製造する方法であって、
(1)以下の成分:
Ag又はAg主体の合金から成る平均粒径が0.3~6.0μmのAg系金属粉末;および、
前記Ag系金属粉末の表面をコーティングするAl,Zr,Ti,Y,Ca,Mg及びZnから成る群から選択されるいずれかを構成要素とする有機系金属化合物若しくは金属酸化物;
ここで、前記有機系金属化合物若しくは前記金属酸化物のコーティング量は、前記Ag系金属粉末100質量部に対し金属酸化物換算で0.02~0.1質量部に相当する量である;
を有するワイヤボンディング部形成用導体ペーストを用意すること、
(2)前記導体ペーストを前記無機基材の表面に塗布して、該無機基材の表面に導体膜を形成すること、
(3)前記形成した導体膜の一部に前記ボンディングワイヤをボンディングすること、
を包含する、電子部品の製造方法。 - 前記導体ペーストは、添加物として無機酸化物粉末及び/又は酸化物ガラス粉末をさらに含んでいる、請求項13に記載の製造方法。
- 前記Ag系金属粉末の平均粒径が3.0~6.0μmのときは、前記導体ペーストは添加物として無機酸化物粉末及び/又は酸化物ガラス粉末をさらに含んでいる、請求項14に記載の製造方法。
- 前記無機基材が結晶質セラミック基材であって、前記導体ペーストは、前記添加物として無機酸化物粉末をさらに含んでいる、請求項15に記載の製造方法。
- 前記無機基材がガラス成分を主成分とする非晶質セラミック基材であって、
前記導体ペーストは、前記添加物として酸化物ガラス粉末をさらに含んでいる、請求項15に記載の製造方法。 - 前記無機酸化物粉末は酸化ビスマスと酸化銅との混合物であって、該混合物の添加量は、前記Ag系金属粉末100質量部に対して0.5~5質量部に相当する量である、請求項14から16のいずれか一項に記載の製造方法。
- 前記酸化物ガラス粉末の添加量は、前記Ag系金属粉末100質量部に対して0.05~0.5質量部に相当する量である、請求項14または15または17に記載の製造方法。
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JP5075222B2 (ja) | 2012-11-21 |
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