WO2012020694A1 - Composition de verre pour électrode, pâte pour électrode utilisant ladite composition de verre, et composant électronique utilisant ladite pâte - Google Patents

Composition de verre pour électrode, pâte pour électrode utilisant ladite composition de verre, et composant électronique utilisant ladite pâte Download PDF

Info

Publication number
WO2012020694A1
WO2012020694A1 PCT/JP2011/067881 JP2011067881W WO2012020694A1 WO 2012020694 A1 WO2012020694 A1 WO 2012020694A1 JP 2011067881 W JP2011067881 W JP 2011067881W WO 2012020694 A1 WO2012020694 A1 WO 2012020694A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
glass composition
weight
particles
glass
Prior art date
Application number
PCT/JP2011/067881
Other languages
English (en)
Japanese (ja)
Inventor
内藤　孝
拓也 青柳
隆彦 加藤
山本　浩貴
正 藤枝
宮田　素之
Original Assignee
株式会社日立製作所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社日立製作所 filed Critical 株式会社日立製作所
Priority to JP2012528656A priority Critical patent/JP5826178B2/ja
Priority to CN201180037099.7A priority patent/CN103052605B/zh
Priority to KR1020137000407A priority patent/KR101414091B1/ko
Publication of WO2012020694A1 publication Critical patent/WO2012020694A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/005—Electrodes
    • H01G4/008—Selection of materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells

Definitions

  • the present invention relates to an electrode glass composition, an electrode paste using the same, and an electronic component to which the paste is applied.
  • Electrodes such as silver (Ag), aluminum (Al), and copper (Cu) are applied to electronic components such as solar cell elements, image display devices, multilayer capacitors, and multilayer circuit boards. These electrodes are generally used as components of electronic components by applying a paste containing metal particles such as Ag, Al, and Cu, glass particles, resin binder and solvent by a printing method and baking the paste. is there.
  • the glass particles are mixed in order to improve and secure the sinterability of the metal particles and the adhesion to the base material by softening and flowing during electrode firing.
  • a glass mainly composed of lead oxide (PbO) having a low transition point that softens and flows at a relatively low temperature is used as the glass particles.
  • lead (Pb) contained in the glass is a harmful substance, and in order to reduce the environmental load, electronic components such as solar cell elements and plasma display panels have bismuth oxide (Bi 2 O 3 ). Pb-free glass mainly composed of is being applied to electrodes.
  • Patent Document 1 Pb-free glass containing Bi 2 O 3 and silicon oxide (SiO 2 ) in an Ag electrode and an Al electrode formed in a solar cell element, and in Patent Document 2, Al formed in a solar cell element.
  • Pb-free glass containing Bi 2 O 3 and boron oxide (B 2 O 3 ) as an electrode has been proposed.
  • Patent Documents 3 and 4 propose a glass mainly composed of vanadium oxide (V 2 O 5 ) for an Ag electrode formed on an electronic component such as a plasma display panel or a multilayer capacitor. These glasses do not contain Bi in addition to Pb.
  • the glass described in Patent Document 3 is composed of V 2 O 5 , phosphorus oxide (P 2 O 5 ), antimony oxide (Sb 2 O 3 ), and barium oxide (BaO).
  • the glass is composed of V 2 O 5 , P 2 O 5 , BaO and sodium oxide (Na 2 O).
  • JIG Joint Industry Guidelines
  • Pb-free glass mainly composed of Bi 2 O 3 is used in electronic parts in place of glass mainly composed of PbO which is harmful as an electrode glass composition in consideration of environmental load.
  • PbO which is harmful as an electrode glass composition in consideration of environmental load.
  • Bi is mined in small quantities as a byproduct of Pb, the extraction of Bi leads to the release of a large amount of Pb.
  • Pb waste is also generated in the purification of Bi. Therefore, the adoption and application of Bi for electronic components are not sufficiently considered to reduce the environmental load.
  • Bi has a small reserve and is unevenly distributed on the earth, so there is a concern from the viewpoint of securing stable raw materials.
  • Patent Documents 3 and 4 propose a glass composition for Ag electrodes that contains Pb and Bi and contains V 2 O 5 as a main component.
  • the electrical resistance as an electrode tends to increase more than when glass containing PbO as a main component is applied due to the reaction. It is difficult to bring out the performance of the electronic components used.
  • As a countermeasure for this there is a method of increasing the film thickness of the electrode, but this causes problems such as an increase in manufacturing cost of the electronic component.
  • An object of the present invention is to provide a glass composition for an electrode that does not substantially contain Pb or Bi and does not deteriorate the performance of the electronic component, an electrode paste using the same, and an electronic component to which the same is applied. It is in.
  • the glass composition for electrodes contains silver, phosphorus and oxygen, and is substantially free of lead.
  • Ag-based, Al-based, Cu-based, etc. electrodes formed on electronic parts do not contain substantially harmful Pb and Bi produced together with the Pb, and the performance of the electronic parts is reduced. It is possible to provide a glass composition for an electrode that is not allowed, and an electrode paste using the same. Thereby, it is possible to provide electronic components such as a solar cell element, an image display device, a multilayer capacitor, and a multilayer circuit board on which electrodes are formed.
  • the present inventor in an electrode containing at least a metal and a glass composition, when the glass composition substantially does not contain Pb and contains at least Ag, P and O, the performance of the electronic component on which the electrode is formed It was found that the impact on the environmental load can be reduced without lowering.
  • the glass composition does not contain Bi.
  • the electrode metal was confirmed to be Ag-based, Al-based, and Cu-based, that is, electrode materials mainly composed of Ag, Al, or Cu.
  • Typical examples of this electronic component include a solar cell element, an image display device, a multilayer capacitor, a multilayer circuit board, and the like.
  • the electrode glass composition is contained in an electrode or electrode paste containing a metal, and contains silver (Ag), phosphorus (P) and oxygen (O), and substantially contains lead (Pb) and It does not contain bismuth (Bi).
  • silver Ag
  • phosphorus P
  • oxygen O
  • substantially contains lead Pb
  • It does not contain bismuth (Bi).
  • substantially not including Pb and Bi is synonymous with not reaching the threshold level described in Non-Patent Document 1. That is, in the present invention, when the content is less than the threshold level, it is accepted as “substantially not contained”.
  • the electrode glass composition preferably further contains vanadium (V).
  • the glass composition for electrodes preferably further contains tellurium (Te).
  • the electrode glass composition further includes at least one metal selected from the group consisting of barium (Ba), tungsten (W), molybdenum (Mo), iron (Fe), manganese (Mn), and zinc (Zn). It is desirable to include an element.
  • Ba barium
  • W tungsten
  • Mo molybdenum
  • Fe iron
  • Mn manganese
  • Zn zinc
  • the preferred composition range of the glass composition for electrodes is 5 to 60% by weight of Ag 2 O, 5 to 50% by weight of P 2 O 5 and 0 to 50% by weight of V 2 O 5 in terms of oxide.
  • TeO 2 is 0 to 30% by weight and other oxides are 0 to 40% by weight. Furthermore, the total of Ag 2 O and V 2 O 5 is 30 to 86% by weight, and P 2 O 5 and TeO The sum of 2 is 14 to 50% by weight.
  • the other oxide is at least one selected from the group consisting of BaO, WO 3 , MoO 3 , Fe 2 O 3 , MnO 2 and ZnO.
  • a more preferable composition range of the glass composition for electrodes is 40 to 70% by weight of Ag 2 O + V 2 O 5 (composition of Ag 2 O and V 2 O 5 ) in terms of oxide, provided that Ag 2 O is 10 to 50% by weight, V 2 O 5 is 20 to 50% by weight, P 2 O 5 + TeO 2 (composition of P 2 O 5 and TeO 2 ) is 25 to 50% by weight, provided that P 2 10-30 wt% for O 5 , 0-30 wt% for TeO 2 , 0-30 wt% for BaO + WO 3 + Fe 2 O 3 + ZnO (composition of BaO, WO 3 , Fe 2 O 3 and ZnO)
  • BaO is 0 to 20 wt%
  • WO 3 is 0 to 10 wt%
  • Fe 2 O 3 is 0 to 10 wt%
  • ZnO is 0 to 15 wt%.
  • the transition point of the glass composition for an electrode is 392 ° C. or lower, preferably 310 ° C. or lower.
  • the electrode glass composition can be effectively applied to an electrode containing one or more metal elements selected from the group consisting of silver (Ag), copper (Cu), and aluminum (Al).
  • the electrode paste includes metal particles containing one or more metal elements of Ag, Al and Cu, particles of the electrode glass composition, a resin binder, and a solvent.
  • the electrode paste preferably contains 0.2 to 20 parts by weight of electrode glass particles with respect to 100 parts by weight of metal particles.
  • the metal particles are Ag particles or particles containing Ag as a main component, it is effective that the amount of electrode glass particles is 3 to 15 parts by weight with respect to 100 parts by weight of the metal particles.
  • the metal particles are Al particles or particles containing Al as a main component, it is effective that the electrode glass particles are 0.2 to 20 parts by weight with respect to 100 parts by weight of the metal particles.
  • the metal particles are Cu particles or Cu-based particles, it is effective that the electrode glass particles are 3 to 15 parts by weight with respect to 100 parts by weight of the metal particles.
  • the electrode paste preferably uses ethyl cellulose or nitrocellulose as the resin binder and butyl carbitol acetate or ⁇ -terpineol as the solvent.
  • the electronic component includes an electrode formed by applying the electrode paste to a substrate or the like and baking it.
  • the electrode after baking contains the metal derived from a metal particle, and the glass composition for electrodes.
  • the resin binder and the solvent are hardly left because they are vaporized by firing. Therefore, the main component of the metal conductor contained in the electrode after firing is Ag in the Ag-based electrode, Al in the Al-based electrode, and Cu in the Cu-based electrode.
  • the glass composition for an electrode contained in the electrode formed on the electronic component is preferably 0.1 to 30% by volume.
  • the electrode is an Ag-based electrode, it is effective that the electrode glass composition contained in the electrode is 5 to 30% by volume.
  • the electrode glass composition contained in the electrode is 0.1 to 15% by volume.
  • the electrode glass composition contained in the electrode is 5 to 20% by volume.
  • examples of the electronic component include a solar cell element, an image display device, a multilayer capacitor, and a multilayer circuit board.
  • the present invention is effective in the case of a solar cell element using a silicon substrate.
  • the glass composition contained in the Al-based electrode of the back surface collecting electrode formed on the p-type upper part is preferably a conductive glass containing a transition metal and P. It is effective that the transition metal in the conductive glass exists in a plurality of oxidation number states, and the existence ratio of the element exhibiting the highest oxidation number state in the transition metal satisfies the relationship of the following formula (1).
  • the left side of the formula (1) is defined as the ion fraction.
  • This ion fraction is determined by pentavalent vanadium (V 5+ ), hexavalent tungsten (W 6+ ), hexavalent molybdenum (Mo 6+ ), and trivalent iron (Fe 3+ ) obtained by each measurement.
  • the sum of the concentrations of tetravalent manganese (Mn 4+ ) divided by the sum of the concentrations of vanadium, tungsten, molybdenum, iron, and manganese in the measurement sample each transition metal exhibits the highest oxidation number state. It is the ratio of existing elements.
  • ⁇ means the concentration of ions or atoms in parentheses (unit: mol / L).
  • the conductive glass contained in the Al-based electrode does not contain any prohibited substances of the RoHS directive, contains V and P as main components, and the mass ratio in terms of oxide of the contained components is expressed by the following formula (2) It is preferable to satisfy the relationship.
  • [] means a mass ratio (unit: mass%) converted to an oxide in parentheses.
  • the conductive glass composition contained in the Al-based electrode is 0.1 to 5% by volume.
  • the electrode paste includes conductive glass particles containing transition metal and P, Al-based particles, a binder resin, and a solvent.
  • the transition metal in the conductive glass particles is present in a plurality of oxidation number states, and it is desirable that the abundance ratio of the element exhibiting the highest oxidation number state in the transition metal satisfies the relationship of the above formula (1).
  • the electrode paste includes conductive glass particles, metal particles, a binder resin, and a solvent, does not include a RoHS directive prohibited substance, the conductive glass particles include V and P as main components, and It is effective that the mass ratio in terms of oxide of the contained component satisfies the relationship of the above formula (2).
  • the solar cell element is characterized in that the back surface output extraction electrode includes a glass composition containing Ag, P and O, which is the glass composition described above, and substantially free of Pb and Bi. It is made of paste.
  • the back surface collecting electrode contains a transition metal and P of the glass composition described later, and this transition metal exists in a plurality of oxidation number states, and the abundance ratio of the elements exhibiting the highest oxidation number state in the transition metal Is preferably formed of an electrode paste containing a conductive glass composition satisfying the relationship of the above formula (1).
  • V As a component of the glass composition contained in the electrode, it was found that V was also effective in addition to Ag, P and O. It has been found that V contained in the glass composition has a function of lowering the firing temperature when forming an electrode on an electronic component, and can improve the moisture resistance, that is, the corrosion resistance of the Al-based electrode. It was also found that Te is preferable as a component of the glass composition although it is a scarce resource and expensive. Te contained in the glass composition, like V, has a function of lowering the firing temperature in forming electrodes on electronic components. In addition to V and Te, it is desirable to include one or more of Ba, W, Mo, Fe, Mn, and Zn, which has been found to contribute to the improvement of electrode reliability, particularly moisture resistance. *
  • Preferred glass composition ranges are 5 to 60% by weight of Ag 2 O, 5 to 50% by weight of P 2 O 5 , 0 to 50% by weight of V 2 O 5 and 0 to 30% by weight of TeO 2 in terms of oxides. %, And other oxides are 0 to 40% by weight. Furthermore, it was found that the total of Ag 2 O and V 2 O 5 is preferably 30 to 86% by weight, and the total of P 2 O 5 and TeO 2 is preferably 14 to 50% by weight.
  • Examples of other oxides include BaO, WO 3 , MoO 3 , Fe 2 O 3 , MnO 2 , ZnO and the like, and it was effective to include one or more of them.
  • TeO 2 exceeds 30% by weight
  • the glass composition increases in cost and the volatilization of the glass component increases during glass production. If the other oxide exceeds 40% by weight, the glass composition may crystallize remarkably, or its softening fluidity may increase remarkably.
  • the softening fluidity of the glass composition is increased in temperature, and the adhesion between the Ag-based electrode and the Cu-based electrode is lowered.
  • the total of Ag 2 O and V 2 O 5 exceeds 86% by weight, the glass composition is easily crystallized, and the moisture resistance of the Ag-based electrode and Cu-based electrode is lowered.
  • a particularly good glass composition range is 40 to 70% by weight of Ag 2 O + V 2 O 5 (composition of Ag 2 O and V 2 O 5 ) in terms of the following oxides, but 10% of Ag 2 O to 50% by weight, V 2 O 5 20 to 50% by weight, P 2 O 5 + TeO 2 (P 2 O 5 and TeO 2 and composition combined) is 25 to 50 wt%, provided that the P 2 O 5 10-30 wt%, TeO 2 0 to 30 wt%, BaO + WO 3 + Fe 2 O 3 + ZnO (BaO and WO 3 and Fe 2 O 3 and composition to suit the ZnO) is 0-30 wt%, however, BaO Was 0 to 20% by weight, WO 3 was 0 to 10% by weight, Fe 2 O 3 was 0 to 10% by weight, and ZnO was 0 to 15% by weight.
  • the transition point of the glass composition is preferably 392 ° C. or less, and if it exceeds this, the adhesion of the electrode may be lowered. In particular, the adhesion of the glass composition having a transition point of 310 ° C. or lower was good.
  • the electrode is coated, dried, and fired using an electrode paste containing metal particles containing any one or more of Ag, Al, and Cu, particles of the glass composition, a resin binder, and a solvent.
  • an electronic component was produced.
  • ethyl cellulose or nitrocellulose is effective as a resin binder
  • butyl carbitol acetate or ⁇ -terpineol is effective as a solvent
  • particles of the glass composition are corroded in an electrode paste. There was hardly anything.
  • the glass composition particles are corroded by a resin binder or solvent, good adhesion may not be obtained during electrode formation.
  • the electrode paste has a range of 0.2 to 20 parts by weight of the glass composition particles of the present invention with respect to 100 parts by weight of the metal particles. all right.
  • the glass composition was less than 0.2 parts by weight, good adhesion could not be obtained.
  • the glass composition exceeds 20 parts by weight, a tendency that the electric resistance is remarkably increased is recognized.
  • the range of 3 to 15 parts by weight of the glass composition particles of the present invention was effective with respect to 100 parts by weight of Ag-based metal particles.
  • the range of 0.2 to 20 parts by weight of the glass composition particles of the present invention was effective with respect to 100 parts by weight of the Al-based metal particles.
  • the range of 3 to 15 parts by weight of the glass composition particles of the present invention was effective with respect to 100 parts by weight of the Cu-based metal particles.
  • an effective glass composition ratio in the electrode is 0.1 to 30% by volume. If the ratio is less than 0.1% by volume, good adhesion cannot be obtained. On the other hand, when the ratio exceeded 30% by volume, the electric resistance tended to increase remarkably.
  • a glass composition ratio of 5 to 30% by volume is effective.
  • Al-based electrodes a glass composition ratio of 0.1 to 15% by volume is effective.
  • Cu-based electrodes glass composition is effective. An effective proportion of the composition was 5-20% by volume. It was found that the effective electrode can be applied to electronic parts such as a solar cell element, an image display device, a multilayer capacitor, and a multilayer circuit board without any problem. In particular, it was effective for solar cells using a silicon substrate. *
  • the glass composition contained in the electrode of the Al-based electrode of the back surface collecting electrode formed on the p-type upper part is a conductive glass containing a transition metal and P.
  • the transition metal in the conductive glass is present in a plurality of oxidation number states, and a glass composition in which the abundance ratio of elements exhibiting the highest oxidation number state in the transition metal satisfies the relationship of the above formula (1) is applied. In this case, it was found that the moisture resistance of the Al-based electrode was remarkably improved and the reliability as a solar cell element was improved.
  • the conductive glass contained in the Al-based electrode does not contain any prohibited substances of the RoHS directive, contains V and P as main components, and the mass ratio in terms of oxide of the contained components is the above formula (2). It was found to be effective when satisfying the relationship. Further, it was found that 0.1 to 5% by volume of the conductive glass composition is effective. When the conductive glass composition was less than 0.1%, good adhesion could not be obtained, and when the conductive glass composition was 5% by volume or more, the specific resistance of the electrode as a solar cell increased.
  • the back surface collecting electrode paste formed on the p-type upper part is an electrode paste containing conductive glass particles containing Al and P, Al-based particles, a binder resin, and a solvent.
  • the transition metal in the conductive glass particles exists in a plurality of oxidation number states and the abundance ratio of the element exhibiting the highest oxidation number state in the transition metal satisfies the relationship of the above formula (1). Reliability as a solar cell element is improved.
  • the electrode paste includes conductive glass particles, metal particles, a binder resin, and a solvent, and does not include any RoHS prohibited substances.
  • the conductive glass particles include V and P as main components, and It is effective that the mass ratio in terms of oxide of the contained component satisfies the relationship of the above formula (2).
  • the back surface output extraction electrode of the solar cell element includes a glass composition containing Ag, P and O, which is the glass composition described above, and substantially free of Pb and Bi.
  • the back surface collecting electrode contains a transition metal and P, which are glass compositions described later, and the transition metal in the conductive glass exists in a plurality of oxidation number states, and has the highest oxidation number among the transition metals.
  • Table 1 shows the composition of glass, its transition point and softening fluidity.
  • the glass of G1 to G37 is a glass of an example containing at least Ag, P, and O without containing Bi that is produced together with substantially harmful Pb and Pb.
  • the glasses G38 to G41 are comparative glasses.
  • G38 is a glass having a very large amount of V 2 O 5 of 55% by weight and a small amount of Ag 2 O.
  • G38 is a glass containing V 2 O 5 as a main component and not containing Ag 2 O.
  • G40 is a glass mainly composed of PbO.
  • G41 is a glass mainly composed of Bi 2 O 3 . Commercially available G40 and G41 glasses were used. On the other hand, the glass of G1-G39 was produced by itself.
  • the production method is as follows: Ag 2 O, P 2 O 5 , V 2 O 5 , TeO 2 , BaCO 3 , WO 3 , MoO 3 , Fe 2 O 3 , MnO 2 and ZnO are used as glass materials, and the glass composition shown in Table 1 is used. A total of about 200 g was prepared and mixed. This was put in a crucible and melted at 800 to 1000 ° C. for 1 hour. Meanwhile, the mixture was stirred to obtain a uniform composition. The melt in the crucible was poured onto a stainless plate to produce glass.
  • Tg transition point
  • softening fluidity a thick powder molded body having a diameter of 10 mm and a thickness of 5 mm was prepared, placed in an electric furnace maintained at 600 ° C., 700 ° C., and 800 ° C. in the air, and held for 5 minutes. The condition was evaluated. ⁇ when good fluidity is obtained, good fluidity is obtained, but ⁇ when crystallization or surface devitrification is observed, softening, but fluidity is insufficient Was evaluated as ⁇ , and when not softened, it was evaluated as ⁇ .
  • DTA differential thermal analysis
  • Tg of G34, G37 and G41 is as high as 400 ° C or higher, the fluidity at 600 ° C was insufficient. However, good fluidity was exhibited at 700 ° C and 800 ° C. Other glasses had low Tg and good fluidity at 600-800 ° C. However, crystallization or surface devitrification occurred for G7, G8, G12, G22 and G33.
  • an electrode paste was prepared using Ag particles, particles of the glass composition shown in Table 1, a resin binder, and a solvent.
  • Spherical particles with an average particle size of 1.4 ⁇ m are used as Ag particles
  • pulverized powder with an average particle size of 3.0 ⁇ m or less is used as glass composition particles
  • ethyl cellulose is used as a resin binder
  • butyl carbitol acetate is used as a solvent. It was.
  • the content of the glass composition particles was 5 parts by weight with respect to 100 parts by weight of the Ag particles.
  • the solid content of the paste containing Ag particles and glass composition particles was set to 70 to 75% by weight.
  • the produced Ag-based electrode paste it was applied to an alumina (Al 2 O 3 ) substrate at a 20 mm square by a printing method.
  • the coating thickness after drying at 150 ° C. was around 20 ⁇ m. After drying at 150 ° C, put it in an electric furnace held at 600 ° C, 700 ° C and 800 ° C in the air, hold it for 5 minutes, take it out, and check the electric resistance, adhesion and moisture resistance of the Ag-based electrode after firing evaluated.
  • the specific resistance at room temperature was measured by the four probe method.
  • the specific resistance was in the range of 10 ⁇ 6 ⁇ cm, it was evaluated as ⁇ , when it was in the range of 10 ⁇ 5 ⁇ cm, ⁇ when it was in the range of 10 ⁇ 4 ⁇ cm, and ⁇ when it was in the range of 10 ⁇ 3 ⁇ cm or more.
  • Adhesiveness was evaluated as ⁇ when the Ag-based electrode was not peeled off when the peeling tape was applied and peeled off, ⁇ when partially peeled, and ⁇ when almost peeled off.
  • Table 2 summarizes the evaluation results of the electrical resistance, adhesion, and moisture resistance of the Ag-based electrode.
  • the Ag-based electrodes of Examples AG1 to AG37 using the glass compositions G1 to G37 do not contain Bi produced with harmful Pb and Pb, and are equivalent. Excellent electrical resistance, adhesion and moisture resistance were achieved.
  • AG34 and AG37 Ag-based electrodes using G34 and G37 glasses having high transition points it was not possible to say that the electrical resistance and adhesion at 600 ° C. were good as in Comparative Example AG41. This is because the firing of the Ag-based electrode does not proceed sufficiently at 600 ° C., and the Ag-based electrode of the example using the glass composition having a transition point of 392 ° C. or lower has good electrical resistance and adhesion. Had.
  • the AG31, AG32, AG35, and AG36 Ag-based electrodes exhibited high electrical resistance when fired at a high temperature of 700 ° C. or 800 ° C. This is presumably because the glass compositions of G31, G32, G35 and G36 increase in resistance by reacting with the Ag particles when these glass compositions are baked at 700 ° C. or higher or 800 ° C. or higher. Further, it can be said that the water resistance of the Ag-based electrodes AG1, AG2, AG4, AG5, AG9 to AG14 and AG21 is not good, as in the case of Comparative Example AG40. That is, the glass compositions of G1, G2, G4, G5, G9 to G14, and G21 were not sufficiently good in water resistance like the glass composition of G40.
  • the Ag-based electrodes of Examples AG1 to AG37 described above include glass compositions of G1 to G37.
  • the common point of these glass compositions is that they contain substantially no harmful Pb and Bi and contain at least Ag, P and O.
  • it contains V and / or Te, or one or more of Ba, W, Mo, Fe, Mn and Zn. This improves the water resistance of the Ag-based electrode.
  • FIG. 1 shows the relationship between the firing temperature and the specific resistance of Ag-based electrodes of representative examples AG4, AG6, AG16, AG20 and AG26 and comparative examples AG40 and AG41.
  • the Ag-based electrode of Comparative Example AG40 using the glass composition G40 containing PbO as the main component is almost stably reduced in resistance in the temperature range of 600 to 800 ° C.
  • the Ag-based electrode of Comparative Example AG41 using the glass composition G41 mainly composed of Bi 2 O 3 has a slightly higher resistance at 600 ° C., but is almost the same as Comparative Example AG40 at 700 ° C. or higher. It shows an equivalent specific resistance.
  • the Ag-based electrode of Example AG20 using a glass composition of G20 shows almost the same specific resistance as Comparative Example AG40, but Examples AG4 using the glass compositions of G4, G6, G16 and G26, AG6, AG16, and AG26 Ag-based electrodes had a slightly lower resistance than those.
  • the Ag-based electrode was polished, and the firing state was observed with a scanning electron microscope (SEM).
  • FIGS. 2A and 2B show SEM images when the Ag-based electrode of Example AG16 is fabricated by firing at 700 ° C. as a representative example.
  • reference numeral 1 denotes Ag sintered particles
  • reference numeral 2 denotes a glass composition for electrodes. Ag particles and their electrodes were densely sintered, and as shown in FIG. 2B, many Ag fine particles 3 were precipitated in the electrode glass composition 2. This is considered to be a result of lower resistance than Comparative Examples AG40 and AG41.
  • the glass compositions of G40 and G41 used in Comparative Examples AG40 and AG41 are insulators. Ag fine particles 3 were observed in the glass composition 2 from any of the Ag-based electrodes of Examples AG4, AG6, AG16, AG20, and AG26, but only Example AG20 had a small amount of precipitation. Therefore, it is considered that the specific resistance was almost the same as that of Comparative Example AG40.
  • the Ag fine particles 3 in the glass composition 2 have a larger amount of Ag 2 O contained in the glass composition, and the lower the transition point, the more the amount of precipitation tends to be. The transition point is 310 ° C. or lower. I liked it.
  • the preferred composition range for the electrode glass composition is 5 to 60% by weight of Ag 2 O, 5 to 50% by weight of P 2 O 5 and V 2 O 5 in terms of the following oxides. 0 to 50 wt%, TeO 2 is 0 to 30 wt%, other oxides are 0 to 40 wt%, and the total of Ag 2 O and V 2 O 5 is 30 to 86 wt%, P 2 The total of O 5 and TeO 2 was 14 to 50% by weight.
  • other oxides include BaO, WO 3 , MoO 3 , Fe 2 O 3 , MnO 2 , and ZnO in the following oxide states, and it is effective to include one or more of them.
  • Ag 2 O + V 2 O 5 composition of Ag 2 O and V 2 O 5
  • the transition point of the glass composition is preferably 392 ° C. or lower, more preferably 310 ° C. or lower.
  • Ag-based electrode paste was prepared using spherical Ag particles having an average particle size of 1.4 ⁇ m as metal particles, ethyl cellulose as a resin binder, and butyl carbitol acetate as a solvent.
  • pulverized powder having an average particle size of 3.0 ⁇ m or less was used for the glass composition of G16.
  • the content of glass composition particles is in the range of 3 to 35 parts by weight with respect to 100 parts by weight of Ag particles, and the content of paste solids containing Ag particles and glass composition particles is 70 to 75% by weight. .
  • Using the produced Ag-based electrode paste it was applied to an alumina (Al 2 O 3 ) substrate at a 20 mm square by a printing method.
  • the coating thickness after drying at 150 ° C. was around 20 ⁇ m. After drying at 150 ° C., it was placed in an electric furnace maintained at 600 ° C., 700 ° C. and 800 ° C. in the air, held for 5 minutes, taken out, and the electrical resistance of the Ag-based electrode after firing was measured.
  • FIG. 3 shows the relationship between the content of G16 glass in the Ag-based electrode and the specific resistance of the Ag-based electrode.
  • the specific resistance of the Ag-based electrode tended to increase as the glass content increased, but the increase in specific resistance was small up to 15 parts by weight and was as good as 10 -6 ⁇ cm. Beyond that content, the resistivity increased by an order of magnitude. Further, when the glass content was low, the influence of the firing temperature on the specific resistance was small, but when the glass content was increased, the specific resistance tended to increase as the firing temperature increased. This is considered to be that the resistance was increased by the reaction between the glass composition of G16 and Ag particles.
  • the minimum glass content was set to 3 parts by weight, but good electrical resistance and adhesion were obtained, so there is a possibility that the glass content can be further reduced.
  • the glass composition is 3 to 15 parts by weight, there is no doubt that it is in a range that can be sufficiently applied as an electrode. This range corresponds to 5 to 30% by volume as the glass composition in the Ag-based electrode.
  • an Al electrode paste was prepared using Al particles, glass composition particles shown in Table 1, resin binder and solvent. Spherical particles having an average particle diameter of 4 ⁇ m were used as Al particles, pulverized powder having an average particle diameter of 3.0 ⁇ m or less was used as glass composition particles, ethyl cellulose was used as a resin binder, and ⁇ -terpineol was used as a solvent.
  • the content of the glass composition particles was 10 parts by weight with respect to 100 parts by weight of the Al particles.
  • the content of the solid content of the paste including Al particles and glass composition particles was set to 70 to 75% by weight.
  • a 20 mm square was applied to a silicon (Si) substrate by a printing method.
  • the coating thickness after drying at 150 ° C. was around 200 ⁇ m.
  • After drying at 150 ° C put it in an electric furnace held at 600 ° C, 700 ° C and 800 ° C in the air, hold it for 5 minutes, take it out, and check the electric resistance, adhesion and moisture resistance of the Al electrode after firing Evaluation was performed in the same manner as in Example 1.
  • Table 3 summarizes the evaluation results of the electrical resistance, adhesion and moisture resistance of the Al-based electrode formed on the Si substrate.
  • Al particles were not sintered at 600 ° C., and good electrical resistance and adhesion could not be obtained. Further, when the firing temperature was increased to 700 ° C. and 800 ° C., the sintering of Al particles proceeded, the electrical resistance was reduced, and the adhesion was improved. Also about this, the difference of the influence by a glass composition was hardly recognized. However, regarding the moisture resistance of the Al electrode, a difference in the glass composition was clearly recognized.
  • Comparative Example AL40 and AL41 Al-based electrodes using conventional glass compositions G40 and G41 mainly composed of PbO or Bi 2 O 3 are corroded by water in the high-temperature and high-humidity test and become black, and have sufficient moisture resistance. It could not be said to have sex.
  • the Al-based electrodes of Examples AL1 to AL37 and Comparative Examples AL38 and AL39, which do not contain harmful Pb and Bi produced with the Pb had equivalent or higher moisture resistance.
  • the moisture resistance was good. This is because V in the glass composition reacts with Al particles, and a layer that is not easily corroded by water is formed on the surface of the Al particles.
  • Fig. 4 shows the results of the study.
  • the specific resistance of the Al-based electrode was hardly different depending on the glass composition, and the resistance decreased as the firing temperature increased.
  • FIGS. 5A and 5B show cross-sectional SEM images of the Al-based electrode of Example AL31 produced by baking at 800 ° C.
  • FIG. 5A and 5B show cross-sectional SEM images of the Al-based electrode of Example AL31 produced by baking at 800 ° C.
  • reference numeral 4 is Al particles
  • reference numeral 5 is a Si substrate
  • reference numeral 6 is an alloy layer (alloy layer by reaction of Al and Si).
  • the glass composition G31 was not clearly observed, but from the surface of the Al particles 4 and the vicinity of the sintered portion thereof, the glass composition G31 A component was detected. From this, the glass composition for electrodes may react with Al particles, and it is considered that the moisture resistance of the Al-based electrode is improved for this reason.
  • the glass composition for an electrode according to the present invention has an electric resistance, adhesion and moisture resistance equal to or better than those of conventional Al-based electrodes. It was found that it can also be applied. *
  • the content of the G31 glass composition particles was in the range of 0.2 to 35 parts by weight with respect to 100 parts by weight of the Al particles.
  • An electrode paste was prepared so that the solid content of the paste containing Al particles and glass composition particles was 70 to 75% by weight.
  • Using the produced Al-based electrode paste it was applied to a silicon (Si) substrate at a 20 mm square by a printing method.
  • the coating thickness after drying at 150 ° C. was around 200 ⁇ m. After drying at 150 ° C., it was placed in an electric furnace maintained at 800 ° C. in the air, held for 5 minutes, then taken out, and the electrical resistance of the Al-based electrode after firing was measured. *
  • FIG. 6 shows the relationship between the content of G31 glass in the Al-based electrode and the specific resistance of the Al-based electrode.
  • the specific resistance of the Al-based electrode tended to increase as the glass content increased, but the specific resistance increased little up to 20 parts by weight of the glass content and was good at the 10 ⁇ 5 ⁇ cm range. Beyond that content, the resistivity increased by an order of magnitude. Since good adhesion and moisture resistance were obtained even when the content of the glass composition was 0.2 parts by weight, the Al-based electrode can be applied in the range of 0.2 to 20 parts by weight. This range corresponds to 0.1 to 15% by volume as the glass composition in the Al-based electrode.
  • an AlCu alloy-based electrode paste was prepared using AlCu alloy particles, glass composition particles shown in Table 1, a resin binder, and a solvent.
  • the AlCu alloy particles had a eutectic composition of 83 atomic% Al and 17 atomic% Cu, the particle shape was spherical, and the average particle size was about 2 to 3 ⁇ m.
  • crushed powder having an average particle size of 3.0 ⁇ m or less was used for the glass composition particles
  • ethyl cellulose was used for the resin binder
  • butyl carbitol acetate was used for the solvent.
  • the content of the glass composition particles was 10 parts by weight with respect to 100 parts by weight of the AlCu alloy particles.
  • the content of paste solids containing AlCu alloy particles and glass composition particles was 70 to 75% by weight.
  • the produced AlCu alloy-based electrode paste was applied to a silicon (Si) substrate by a printing method with a 20 mm square.
  • the coating thickness after drying at 150 ° C. was around 40 ⁇ m. After drying at 150 ° C, put it in an electric furnace held at 600 ° C, 700 ° C and 800 ° C in the air, hold it for 5 minutes, take it out, and fire the AlCu alloy electrode after firing, electrical resistance, adhesion and moisture resistance Were evaluated in the same manner as in Examples 1 and 3.
  • Table 4 summarizes the evaluation results of electrical resistance, adhesion and moisture resistance of the AlCu alloy-based electrode formed on the Si substrate.
  • the electrical resistance at 600 ° C. and 700 ° C. was lowered and the adhesion at 600 ° C. was improved in both the AlCu alloy-based electrodes of Examples and Comparative Examples. This is because the melting point was lowered by using the CuAl eutectic composition for the CuAl alloy particles, and the sintering of the metal particles proceeded. Almost no influence by the glass composition contained in the electrical resistance and adhesion of the AlCu alloy-based electrode was observed, but with respect to moisture resistance, as in Example 3, the influence by the glass composition was remarkably recognized. It was.
  • Comparative examples AC40 and AC41 AlCu alloy electrodes using conventional glass compositions G40 and G41 mainly composed of PbO or Bi 2 O 3 are corroded by water in a high-temperature and high-humidity test. It could not be said that it had high moisture resistance.
  • the AlCu alloy-based electrodes of Examples AC1 to AC37 and Comparative Examples AC38 and AC39 not containing harmful Pb and Bi produced together with the Pb had equivalent or higher moisture resistance.
  • the moisture resistance was good as in Example 3.
  • the moisture resistance at 600 ° C. was improved. This is considered to be because V in the glass composition reacts with the AlCu alloy particles and a layer that is not easily corroded by water is formed on the surface of the AlCu alloy particles.
  • Fig. 7 shows the result of the study.
  • the specific resistance of the AlCu alloy-based electrode showed almost no difference depending on the glass composition, and the resistance decreased as the firing temperature increased, and a good electrical resistance was exhibited at 700 ° C. or higher. Further, the electric resistance was lower than that of the Al-based electrode shown in FIG. *
  • the glass composition for electrodes of the present invention has electrical resistance, adhesion and moisture resistance that are equal to or better than those of AlCu alloy electrodes using conventional glass compositions for electrodes. Therefore, it was found that the present invention can also be applied to AlCu alloy-based electrodes, such as the Ag-based electrode shown in Example 1 and the Al-based electrode shown in Example 3. *
  • the content of G32 glass composition particles is in the range of 0.2 to 35 parts by weight with respect to 100 parts by weight of AlCu alloy particles, and the content of paste solids containing AlCu alloy particles and glass composition particles is 70 to 75 parts.
  • An electrode paste was prepared so as to have a weight%.
  • the produced AlCu alloy-based electrode paste was applied to a silicon (Si) substrate by a printing method with a 20 mm square.
  • the coating thickness after drying at 150 ° C. was around 40 ⁇ m. After drying at 150 ° C., it was placed in an electric furnace maintained at 700 ° C. in the air, held for 5 minutes, then taken out, and the electrical resistance of the fired AlCu alloy electrode was measured. *
  • FIG. 8 shows the relationship between the content of G32 glass in the AlCu alloy-based electrode and the specific resistance of the AlCu alloy-based electrode.
  • the specific resistance of the AlCu alloy-based electrode tended to increase as the glass content increased.
  • the increase in specific resistance was small up to a glass content of 20 parts by weight, which was as good as 10 ⁇ 5 ⁇ cm. Beyond that content, the resistivity increased by an order of magnitude. Since good adhesion and moisture resistance were obtained even when the content of the glass composition was 0.2 parts by weight, the AlCu alloy-based electrode can be applied in the range of 0.2 to 20 parts by weight. This range corresponds to 0.2 to 17% by volume as the glass composition in the AlCu alloy-based electrode.
  • a Cu-based electrode paste was prepared using Cu particles, glass composition particles shown in Table 1, a resin binder, and a solvent.
  • the content of the glass composition particles was 7 parts by weight with respect to 100 parts by weight of the Cu particles.
  • the paste solid content containing Cu particles and glass composition particles was 70 to 75% by weight.
  • the produced Cu-based electrode paste was applied to an alumina (Al 2 O 3 ) substrate at a 20 mm square by a printing method.
  • the coating thickness after drying at 110 ° C. was around 30 ⁇ m.
  • After drying at 110 ° C put it in an electric furnace held at 600 ° C, 700 ° C and 800 ° C in nitrogen respectively, hold it for 5 minutes, take it out, and check the electrical resistance, adhesion and moisture resistance of the Cu-based electrode after firing Evaluation was performed in the same manner as in Example 1.
  • Table 5 summarizes the evaluation results of electrical resistance, adhesion, and moisture resistance of the Cu-based electrode formed on the alumina substrate.
  • the Cu-based electrodes of Comparative Examples CU40 and CU41 using the conventional glass compositions G40 and G41 mainly composed of PbO or Bi 2 O 3 exhibit almost good electrical resistance and adhesion.
  • the electrical resistance of CU41 at 800 ° C. was good, but at 600 ° C., the firing did not proceed sufficiently and the electrical resistance was high. For this reason, the adhesion at 600 ° C. was not good.
  • the moisture resistance of G41 itself is good, the CU-based electrode CU41 using the glass composition was also good.
  • G40 cannot be said to be a glass having good moisture resistance, and the moisture resistance was not sufficiently good even in the Cu-based electrode CU40 containing it.
  • the Cu-based electrodes of Examples CU1 to CU37 described above include G1 to G37 electrode glass compositions, and the common points of these glass compositions are substantially free of harmful Pb and Bi, and at least It contains Ag, P and O. More preferably, when one or more of V, Te, Ba, W, Mo, Fe, Mn, and Zn are included, the water resistance of the Cu-based electrode is good.
  • the adhesion and moisture resistance were equivalent to those of Comparative Example CU40, but the electrical resistance was very large and could not be applied to the electrode. There wasn't.
  • the glass composition of G39 is a V 2 O 5 —P 2 O 5 system that does not contain Ag 2 O, so that it reacts with the Cu particles to significantly increase the resistance. Further, in the Cu-based electrode of Comparative Example CU38 using a glass composition G38 with a small amount of Ag 2 O and a large amount of V 2 O 5 , G38 reacts with Cu particles, although not as much as Comparative Example CU39. The resistance was increased.
  • FIG. 9 shows the relationship between the firing temperature and the specific resistance for Cu-based electrodes of representative examples CU16 and CU33 and comparative examples CU40 and CU41.
  • the Cu-based electrodes of Examples CU16 and CU33 and Comparative Examples CU40 and CU41 decreased in specific resistance as the firing temperature increased. Resistance was small and good.
  • the Cu-based electrodes of Examples CU16 and CU33 were good in both adhesion and moisture resistance, unlike the Cu-based electrodes of Comparative Examples CU40 and CU41. That is, rather than using a conventional glass composition mainly composed of PbO or Bi 2 O 3 for a Cu-based electrode, the glass composition for an electrode of the present invention containing no harmful Pb or Bi produced with the Pb is used. It is more advantageous to apply to Cu-based electrodes.
  • the content of G16 glass composition particles is in the range of 3 to 35 parts by weight with respect to 100 parts by weight of Cu particles, and the content of paste solids containing Cu particles and glass composition particles is 70 to 75% by weight.
  • An electrode paste was prepared so that Using the produced Cu-based electrode paste, it was applied to an alumina (Al 2 O 3 ) substrate at a 20 mm square by a printing method. The coating thickness after drying at 110 ° C. was around 30 ⁇ m. After drying at 110 ° C., it was placed in an electric furnace maintained at 800 ° C. in nitrogen, held for 5 minutes, taken out, and the electrical resistance of the Cu-based electrode after firing was measured.
  • FIG. 10 shows the relationship between the content of G16 glass in the Cu-based electrode and the specific resistance of the Cu-based electrode.
  • the specific resistance of the Cu-based electrode tended to increase as the glass content increased, but the increase in specific resistance was small up to 15 parts by weight and was good at 10 -6 ⁇ cm. Beyond that content, the resistivity increased by an order of magnitude. Although the minimum glass content was 3 parts by weight, there was a possibility that the glass content could be further reduced because good electrical resistance and adhesion were obtained. However, if the glass composition is 3 to 15 parts by weight, there is no doubt that it is in a range that can be sufficiently applied as an electrode. This range corresponds to 5 to 20% by volume as the glass composition in the Cu-based electrode.
  • the electrode glass composition of the present invention and the electrode paste containing the same are more harmful than the conventional electrode glass compositions mainly containing PbO and Bi 2 O 3 and the electrode paste containing the same. Even if Pb and Bi are not included, the same or better electrode characteristics can be expressed. That is, it can be effectively applied to various electrodes such as Ag-based, Al-based, and Cu-based electrodes while reducing the influence on the environmental load.
  • the electrode according to the present invention was actually attached to a representative electronic component, and its applicability was confirmed.
  • 11 to 13 schematically show the cross section, light receiving surface and back surface of the manufactured solar cell element.
  • the semiconductor substrate 10 (also referred to simply as “substrate”) of the solar cell element.
  • the semiconductor substrate 10 contains boron (B) or the like and is a p-type semiconductor.
  • B boron
  • the light-receiving surface is doped with phosphorus (P) or the like to form an n-type semiconductor diffusion layer 11 with a thickness of the order of submicron, and a pn junction is formed at the boundary with the p-type bulk portion.
  • an antireflection layer 12 such as Si 3 N 4 is formed on the light receiving surface with a film thickness of about 100 nm by vapor deposition or the like.
  • the light-receiving surface electrode 13 and the output extraction electrode 15 use an Ag-based electrode paste containing powder of the electrode glass composition, and the current collecting electrode 14 is an Al-based electrode paste containing powder of the electrode glass composition Is used. These are applied by screen printing. After drying, firing is performed at about 800 ° C. in the atmosphere, and each electrode is formed on the semiconductor substrate 10. At that time, on the light receiving surface, the glass composition contained in the light receiving surface electrode 13 reacts with the antireflection layer 12, and the light receiving surface electrode 13 and the diffusion layer 11 are electrically connected.
  • Al in the current collecting electrode 14 diffuses to the back surface of the semiconductor substrate 10 to form an electrode component diffusion layer 16, so that between the semiconductor substrate 10 and the current collecting electrode 14 and the semiconductor substrate 10. And an output extraction electrode 15 can be obtained ohmic contact.
  • a polycrystalline Si substrate (p-type semiconductor) containing B as the semiconductor substrate 10 was used.
  • the size of the semiconductor substrate 10 was 150 mm square and the thickness was 200 ⁇ m, and the surface was etched with a strong alkaline aqueous solution to form irregularities.
  • a diffusion layer 11 (n-type semiconductor layer) having a thickness of about 0.8 ⁇ m is formed by doping P on the light receiving surface, and an antireflection layer 12 is formed thereon by depositing Si 3 N 4 to a thickness of about 100 nm. Formed.
  • the light-receiving surface electrode 13 and the output extraction electrode 15 were formed using an Ag-based electrode paste containing a glass composition for G4, G16, G20, G40 or G41 shown in Table 1. These electrode glass compositions were mixed with 7 parts by weight of 100 parts by weight of Ag particles using pulverized powder having an average particle size of 3 ⁇ m or less, as in Example 1. The same Ag particles, resin binder and solvent as in Example 1 were used, and the paste for the Ag electrode so that the paste solid content containing Ag particles and glass composition particles was 70 to 75% by weight. Was made.
  • the current collecting electrode 14 was formed by using an Al-based electrode paste containing a glass composition for G4, G16, G28, G40 or G41 shown in Table 1. These electrode glass compositions were mixed with 1 part by weight of 100 parts by weight of Al particles using pulverized powder having an average particle size of 3 ⁇ m or less in the same manner as in Example 3. The same Al particles, resin binder and solvent as in Example 3 were used, and the paste for the Al electrode was such that the solid content of the paste containing Al particles and glass composition particles was 70 to 75% by weight. Was made. The prepared Ag electrode paste and Al electrode paste were applied by screen printing and dried. The film thickness after drying was about 20 ⁇ m for the Ag-based electrode paste and about 40 ⁇ m for the Al-based electrode paste.
  • the conversion efficiency of the solar cell element produced as described above was measured with a solar simulator.
  • At least one of the light receiving surface electrode, the back surface output extraction electrode, and the back surface collecting electrode in the examples of Table 6 uses the glass of the examples shown in Table 1.
  • the light receiving surface electrode, the back surface output extraction electrode, and the back surface collecting electrode of the comparative example in Table 6 all use the glass of the comparative example shown in Table 1.
  • Comparative Example S6 is a glass composition for electrodes mainly composed of conventional PbO as an Ag-based electrode that is a light-receiving surface electrode, an Ag-based electrode that is a back surface output extraction electrode, and an Al-based electrode that is a back surface collecting electrode.
  • Material G40 was used. The element conversion efficiency was 16.5%.
  • Comparative Example S7 using the conventional glass composition G41 mainly composed of Bi 2 O 3 for each electrode, the device conversion efficiency was 14.4%, which was very low compared to Comparative Example S6. .
  • the element conversion efficiency of Comparative Example S8 using G40 for the Ag-based electrode and G41 for the Al-based electrode was 16.0% between Comparative Examples S6 and S7.
  • the element conversion efficiency varies depending on the electrode glass composition, and the glass composition containing PbO as the main component has higher element conversion efficiency than the glass composition containing Bi 2 O 3 as the main component.
  • Example S1 to S3 In contrast to these comparative examples S6 to S8, in Examples S1 to S3, the glass composition for an electrode of the present invention was used for all of the light-receiving surface Ag-based electrode, the output extraction Ag-based electrode, and the collecting Al-based electrode.
  • the element conversion efficiencies of Examples S1 to S3 were larger than those of Comparative Examples S7 and S8, and were almost equivalent to Comparative Example S6. In other words, it has been found that harmful Pb and Bi can be removed from the solar cell element and its electrode without substantially degrading the element conversion efficiency. *
  • Examples S4 and S5 are cases where both the glass composition for an electrode of the present invention and the conventional glass composition for an electrode mainly composed of PbO are used, but the element conversion efficiency of Examples S4 and S5 is It was the same as Examples S1 to S3 and was almost equivalent to Comparative Example S6. That is, it was also found that harmful Pb and Bi can be reduced by using the electrode glass composition of the present invention for either an Ag-based electrode or an Al-based electrode.
  • the glass composition for an electrode of the present invention and the electrode paste using the same can be applied to an electrode of a solar cell element with sufficient consideration to the influence on the environmental load.
  • a plasma display was manufactured using the electrode glass composition of the present invention and the electrode paste using the same.
  • FIG. 14 shows an outline of a sectional view of the manufactured PDP.
  • the front plate 20 and the back plate 21 are arranged to face each other with a gap of 100 to 150 ⁇ m, and the gap between the substrates is maintained by the partition wall 22.
  • the peripheral portions of the front plate 20 and the back plate 21 are hermetically sealed with a sealing material 23, and the inside of the panel is filled with a rare gas.
  • the minute spaces (cells 24) partitioned by the barrier ribs 22 are filled with red, green and blue phosphors 25, 26 and 27, respectively, and one pixel is constituted by three color cells. Each pixel emits light of each color according to the signal.
  • the front plate 20 and the back plate 21 are provided with electrodes regularly arranged on a glass substrate.
  • the display electrode 28 on the front plate 20 and the address electrode 29 on the back plate 21 are paired, and a voltage of 100 to 200 V is selectively applied between them according to the display signal, and ultraviolet rays 30 are generated by the discharge between the electrodes.
  • the red, green and blue phosphors 25, 26 and 27 are caused to emit light to display image information.
  • the display electrodes 28 and the address electrodes 29 are covered with dielectric layers 32 and 33 in order to protect these electrodes and control wall charges during discharge. A thick glass film is used for the dielectric layers 32 and 33.
  • the back plate 21 is provided with a partition wall 22 on the surface of the dielectric layer 33 of the address electrode 29 in order to form the cell 24.
  • the partition wall 22 is a stripe-shaped or box-shaped structure.
  • a black matrix 31 black band may be formed between the display electrodes 28 of the adjacent cells 24.
  • an Ag-based electrode wiring containing an electrode glass composition mainly composed of PbO or Bi 2 O 3 is applied.
  • This Ag-based electrode is formed by applying an electrode paste containing Ag fine particles, electrode glass composition fine particles, and a photosensitizer by a printing method, attaching an electrode mask after drying, and irradiating with ultraviolet rays. An electrode is formed by removing an unnecessary part and baking.
  • the display electrodes 28, the address electrodes 29, and the black matrix 31 can be formed by a sputtering method, but a printing method is advantageous for reducing the cost.
  • the dielectric layers 32 and 33 are generally formed by a printing method.
  • the display electrode 28, the address electrode 29, the black matrix 31, and the dielectric layers 32 and 33 formed by a printing method are generally baked in a temperature range of 450 to 620 ° C. in an oxidizing atmosphere such as air. .
  • a dielectric layer 32 is formed on the entire surface.
  • a protective layer 34 is formed on the surface of the dielectric layer 32 in order to protect the display electrodes 28 and the like from discharge. In general, a deposited film of magnesium oxide (MgO) is used for the protective layer 34.
  • a partition wall 22 is provided on the surface of the dielectric layer 33 of the back plate 21.
  • the partition wall 22 made of a glass structure is made of a structural material containing at least a glass composition and a filler, and is composed of a fired body obtained by sintering the structural material.
  • the partition wall 22 is formed by attaching a volatile sheet having a groove cut to the partition wall portion, pouring a partition wall paste into the groove, and baking at 500 to 600 ° C., thereby volatilizing the sheet and forming the partition wall 22. Can do.
  • the barrier rib 22 may be formed by applying barrier rib paste over the entire surface by printing, masking after drying, removing unnecessary portions by sandblasting or chemical etching, and baking at 500 to 600 ° C. it can.
  • the cells 24 separated by the barrier ribs 22 are filled with pastes of phosphors 25, 26, and 27 of each color and fired at 450 to 500 ° C., thereby red, green, and blue phosphors 25, 26, 27 is formed respectively.
  • the front plate 20 and the back plate 21 produced separately are opposed to each other and aligned accurately, and the periphery is glass sealed at 420 to 500 ° C.
  • the sealing material 23 is previously formed on the peripheral edge of either the front plate 20 or the back plate 21 by a dispenser method or a printing method. In general, the sealing material 23 is formed toward the back plate 21. Further, the sealing material 23 may be temporarily fired in advance simultaneously with the firing of the red, green and blue phosphors 25, 26 and 27. By adopting this method, it is possible to remarkably reduce bubbles in the glass sealing portion, and a highly airtight, that is, highly reliable glass sealing portion is obtained.
  • a voltage is applied at a portion where the display electrode 28 and the address electrode 29 intersect, and the rare gas in the cell 24 is discharged to form a plasma state. Then, using the ultraviolet light 30 generated when the rare gas in the cell 24 returns from the plasma state to the original state, the red, green and blue phosphors 25, 26, 27 are emitted to light the panel, Display image information.
  • address discharge is performed between the display electrode 28 and the address electrode 29 of the cell 24 to be lit, and wall charges are accumulated in the cell 24.
  • display discharge occurs only in the cells where the wall charges are accumulated by the address discharge, and the ultraviolet light 30 is generated to cause the phosphor to emit light. Display is performed.
  • the PDP shown in FIG. 14 was manufactured by applying the Ag-based electrode paste prepared using the electrode glass composition of the present invention to the display electrode 28 of the front plate 20 and the address electrode 29 of the back plate 21.
  • the electrode glass composition of the present invention fine particles obtained by grinding G16 shown in Table 1 to an average particle size of about 1 ⁇ m were used.
  • the Ag particles spherical fine particles having an average particle diameter of about 1 ⁇ m were used.
  • an electrode mask was attached to the coated surface and irradiated with ultraviolet rays to remove excess portions, and display electrodes 28 and address electrodes 29 were formed on the front plate 20 and the back plate 21. Then, it put into the electric furnace, heated to 600 degreeC with the temperature increase rate of 5 degree-C / min in air
  • the black matrix 31 and dielectric layers 32 and 33 are applied, heated to 560 ° C. at a heating rate of 5 ° C./min in the atmosphere, held for 30 minutes, and then cooled in the furnace. Was baked.
  • the front plate 20 and the back plate 21 were separately manufactured, and the outer peripheral portion was glass-sealed to manufacture the PDP shown in FIG.
  • Each of the electrodes according to the present invention could be applied to the PDP in a good appearance with no appearance of discoloration or void due to reaction or oxidation in both the display electrode 28 and the address electrode 29.
  • the PDP address electrode 29 shown in FIG. 14 may have a higher electrical resistance than the display electrode 28.
  • the PDP of FIG. 14 was manufactured in the same manner as in Example 7, and a lighting experiment was performed. Further, the Ag electrode according to the present invention used in Example 7 was applied to the display electrode 29.
  • an AlCu alloy electrode paste containing particles of the glass composition for an electrode of the present invention AlCu alloy particles, a photosensitizer, a resin binder and a solvent was used.
  • AlCu alloy particles fine particles obtained by pulverizing G19 shown in Table 1 to an average particle diameter of about 2 ⁇ m are used, and for AlCu alloy particles, spherical fine particles having an average particle diameter of 1 to 2 ⁇ m are used. 10 parts by weight of fine particles of the electrode glass composition G19 of the present invention were blended with 100 parts by weight of fine particles. Further, ethyl cellulose was used as the resin binder, and butyl carbitol acetate was used as the solvent.
  • This AlCu alloy-based electrode paste was applied to the entire surface of the back plate 21 by screen printing and dried at 150 ° C. in the atmosphere. The film thickness after drying was about 10 ⁇ m.
  • Example 7 An electrode mask was attached to the coated surface, and the excess portions were removed by irradiating with ultraviolet rays, and the address electrode 29 was baked and formed on the back plate 21 in the same manner as in Example 7.
  • a dielectric layer 33, barrier ribs 22, and phosphors 25, 26, and 28 were sequentially formed thereon, and a back plate 21 was produced.
  • the back plate 21 and the front plate 20 produced in Example 7 were opposed to each other, and the outer peripheral portion was glass-sealed to produce the PDP shown in FIG.
  • the AlCu alloy-based electrode according to the present invention applied to the address electrode 29 was in a good state in appearance with no discoloration or void formation due to reaction or oxidation.
  • the panel could be turned on without increasing the electrical resistance of the address electrode 29 and without decreasing the withstand voltage.
  • the electrode glass composition of the present invention and the AlCu alloy electrode paste using the same were applicable as the address electrode 29 of the PDP.
  • harmful Pb and Bi produced with Pb are not included, the impact on the environmental load can be reduced.
  • it can be an alternative to Ag-based electrodes, which can contribute to cost reduction.
  • LTCC Low Temperature Co-fired Ceramics
  • FIG. 15 shows an outline of a sectional view of the manufactured LTCC. *
  • the wiring 40 is three-dimensionally formed between the plurality of ceramic layers 41.
  • the wiring 40 is electrically connected by a connection wiring 42 that penetrates the ceramic layer 41.
  • a green sheet containing a mixture of ceramic powder and glass powder is produced, and a through hole is formed at a desired position.
  • an electrode paste for forming the wiring 40 is applied by a printing method and filled into the through holes.
  • an electrode paste for forming the wiring 40 may also be applied to the back surface of the green sheet by a printing method.
  • the electrode paste applied to the surface is dried.
  • the green sheets on which the electrode paste is formed are stacked and usually fired at around 900 ° C.
  • the firing atmosphere is generally in the air when an Ag-based wiring is applied, or in nitrogen or an atmosphere containing water vapor when a Cu-based wiring is applied. By firing, the green sheet becomes the ceramic layer 41, and the electrode paste filled in the through hole becomes the connection wiring.
  • Ag spherical fine particles having an average particle diameter of about 1 ⁇ m, fine particles of an electrode glass composition G4 having an average particle diameter of about 2 ⁇ m, ethyl cellulose as a resin binder, and butyl carbitol acetate as a solvent were used.
  • 3 parts by weight of fine particles of the electrode glass composition G4 of the present invention were blended with 100 parts by weight of Ag fine particles.
  • Cu-based electrode paste Cu spherical fine particles having an average particle diameter of about 2 ⁇ m, electrode glass composition G20 fine particles having an average particle diameter of about 2 ⁇ m, nitrocellulose as a resin binder, and butyl carbitol acetate as a solvent were used. . Further, 5 parts by weight of the fine particles of the electrode glass composition G20 of the present invention were blended with 100 parts by weight of the Cu fine particles. *
  • the wiring 40 was formed using these electrode pastes.
  • the firing conditions were 900 ° C. in the air when applying the Ag-based electrode paste, and 950 ° C. in nitrogen containing water vapor when applying the Cu-based electrode paste.
  • the holding time was 60 minutes.
  • the two types of LTCC produced were both fired densely.
  • the wiring 30 was hardly discolored due to reaction or oxidation or generation of voids, and was able to be applied to LTCC in a good appearance.
  • the LTCC to which the Cu-based electrode including the glass composition for electrode G20 of the present invention is applied is an Ag-based electrode including the glass composition for electrode G4 of the present invention.
  • the electrical resistance of the wiring was slightly higher than that of LTCC to which No. was applied, it was more advantageous for migration between wiring than LTCC to which Ag-based electrodes were applied. Both were applicable to LTCC. In addition, since it does not contain harmful Pb or Bi, the impact on the environmental load could be reduced.
  • FIG. 16 shows a cross section of the manufactured multilayer capacitor. *
  • a plurality of internal electrodes 51 are disposed in a ferroelectric glass ceramic 50 having a very large dielectric constant, and external electrodes 52 that are electrically connected to the internal electrodes 51 are formed at both ends thereof.
  • the internal electrode 51 and the external electrode 52 are formed by applying and baking an Ag-based electrode paste containing particles of an electrode glass composition mainly composed of PbO or Bi 2 O 3 .
  • the firing conditions differ depending on the ferroelectric glass ceramic 50 to be applied, but are generally heated at about 800 to 1100 ° C. in the atmosphere.
  • an Ag-based electrode paste containing the electrode glass composition of the present invention was prepared and applied to the internal electrode 51 and the external electrode 52.
  • Ag spherical fine particles having an average particle diameter of about 1 ⁇ m, electrode glass composition G27 fine particles having an average particle diameter of about 2 ⁇ m, ethyl cellulose as a resin binder, and butyl carbitol acetate as a solvent were used.
  • 5 parts by weight of fine particles of the electrode glass composition G27 of the present invention were blended with 100 parts by weight of Ag fine particles.
  • the internal electrode 51 and the external wiring 52 were applied and formed using this Ag-based electrode paste, and fired at 950 ° C. in the atmosphere.
  • the holding time was 30 minutes.
  • the manufactured multilayer capacitor was fired densely.
  • the internal electrode 51 and the external wiring 52 were hardly discolored due to reaction or oxidation and the generation of voids was not recognized, and could be applied in a good appearance.
  • the multilayer capacitor to which the Ag-based electrode containing the electrode glass composition G27 of the present invention is applied is a conventional Ag capacitor containing an electrode glass composition mainly composed of PbO or Bi 2 O 3.
  • the dielectric characteristics and the reliability such as moisture resistance are equal to or higher than those of the multilayer capacitor. Therefore, it was found that the present invention can be applied to the multilayer capacitor and the like. In addition, since it does not contain harmful Pb or Bi, the impact on the environmental load could be reduced.
  • the present invention is not limited to the solar cell element, the image display device, the multilayer circuit board, and the multilayer capacitor, but includes an electrode including a glass composition. It can be used for electronic parts in general. Moreover, since the glass composition for electrodes of the present invention has a low transition point and low meltability, it may be applicable to other than electrodes. For example, adhesion at low temperature, sealing, coating and the like can be mentioned.
  • Table 7 shows the conductive glass composition studied for the back collector electrode, its softening point and ion fraction.
  • the raw materials for glass include V 2 O 5 , P 2 O 5 , Sb 2 O 3 , MnO 2 , Fe 2 O 3 , Bi 2 O 3 , Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , BaCO 3 , ZnO, WO 3 , TeO 2 , CuO, MoO 3 and B 2 O 3 were used, and about 200 g of glass composition ratios shown in Table 7 were prepared.
  • the mixture was put in a crucible and placed at 900 ° C to 1500 ° C. Melted for hours. Then, the glass powder was produced similarly to Example 1, and the softening point of glass was measured by DTA.
  • FIG. 17 shows a typical DTA curve of glass.
  • the glass softening point generally refers to the second endothermic peak of the glass composition shown in FIG. *
  • the transition metal in the prepared conductive glass conforms to JIS-G1221, JIS-G1220, JIS-G1218, JIS-H1353 and JIS-G1213. Then, it was measured by a redox titration method.
  • an Al-based electrode paste was prepared using Al particles, particles of the conductive glass composition prepared in Table 7, a resin binder, and a solvent.
  • the Al particles are spherical particles having an average particle diameter of 4 ⁇ m used in Example 3, the conductive glass composition particles are pulverized powder having an average particle diameter of 3.0 ⁇ m or less, the resin binder is ethyl cellulose, and the solvent is butyl carbitol acetate.
  • the content of the conductive glass composition particles was 0.5 parts by weight with respect to 100 parts by weight of the Al particles.
  • the paste solid content containing Al particles and conductive glass composition particles was 70 to 75% by weight.
  • a solar cell element was produced in the same manner as in Example 6 using the produced Al-based electrode paste.
  • an Ag-based electrode paste AG4 containing the G4 electrode glass composition shown in Table 1 was used.
  • the collector electrode 14 is formed by using the electrode-based glass compositions G4, G16, G40 and G41 shown in Table 1 or the Al-based electrode pastes AN42 to AN79 containing the conductive glass compositions N42 to N79.
  • the Al-based electrode pastes AN4, AN16, AN40 and AN41 were used.
  • the prepared Ag-based electrode paste and Al-based electrode paste were each applied by screen printing and dried.
  • the film thickness after drying was about 20 ⁇ m for the Ag-based electrode paste and about 40 ⁇ m for the Al-based electrode paste.
  • it was rapidly heated to 800 ° C in the atmosphere in a tunnel furnace and then rapidly cooled.
  • the light receiving surface electrode 13 was fired on the light receiving surface, and the output extraction electrode 15 and the current collecting electrode 14 were simultaneously fired on the back surface to form the respective electrodes, thereby producing a solar cell element.
  • the electrical resistance, adhesion and moisture resistance of the Al-based electrode of the solar cell element produced as described above were evaluated.
  • the specific resistance at room temperature was measured by the four probe method. At this time, relative evaluation was performed assuming that the specific resistance of AN40 was 100.
  • the adhesion and moisture resistance were evaluated in the same manner as in Example 1.
  • the conductive glass composition that was equal to or less than the reference AN40 had an ion fraction greater than 0.5, that is, It was found that the above formula (1) was satisfied.
  • the ion fraction is> 0.6, and more preferably, the ion fraction is> 0.7.
  • the conductive glass composition that was equal to or less than that of the reference AN40 had a component content in an oxide equivalent mass ratio. It was found that the relationship of the above formula (2) was satisfied.
  • the softening point was 450 ° C. or less.
  • the relationship between moisture resistance and the conductive glass composition and softening point revealed that the moisture resistance is good in the case of a conductive glass composition having a softening point of 500 ° C. or lower and containing V 2 O 5. did.
  • Example 11 4 ⁇ m Al spherical particles were used for the metal particles, pulverized powder having an average particle size of 3.0 ⁇ m or less for the conductive glass composition particles, ethyl cellulose for the resin binder, and butyl carbitol acetate for the solvent.
  • an Al-based electrode paste was prepared.
  • the content of conductive glass composition particles is 0.05 to 20 parts by weight with respect to 100 parts by weight of Al particles, and the content of paste solids containing Al particles and conductive glass composition particles is 70 to 75 parts. % By weight.
  • a solar cell element was produced using the produced Al-based electrode paste in the same manner as in Example 11, and the electrical resistance of the fired Al-based electrode was measured. *
  • FIG. 18 shows the relationship between the N58 conductive glass content in the Al-based electrode and the specific resistance of the Al-based electrode.
  • the specific resistance of Al-based electrodes tended to increase with increasing conductive glass content.
  • the conductive glass content is 6 parts by weight or less, the specific resistance is 10 ⁇ 4 ⁇ cm or less, which is desirable as an electrode.
  • the conductive glass content is less than 0.1 parts by weight, there has been a problem that the electrode is peeled off. Therefore, if the conductive glass content is 0.1 to 6 parts by weight, the electrode is within a preferable range. There is no doubt that there is. This range corresponded to 0.1 to 5% by volume as the glass composition in the Al-based electrode.
  • solar cell elements were produced when the electrode paste of the present invention was variously combined with the light-receiving surface electrode 13, the back surface output extraction electrode 15, and the collector electrode 14.
  • the method for producing the solar cell element was produced in the same manner as in Example 6.
  • the same Ag-based electrode paste as in Example 6 containing the glass compositions for electrodes G4 and G40 shown in Table 1 was used.
  • the current collecting electrode 14 was formed for an Al-based electrode similar to Example 11 including the N42 and N58 conductive glass compositions shown in Table 7 and the G40 and G41 electrode glass compositions shown in Table 1. A paste was used. *
  • the conversion efficiency of the manufactured solar cell element was evaluated by a solar simulator. At this time, the appearance of the solar cell element was also evaluated.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Computer Hardware Design (AREA)
  • Sustainable Energy (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Conductive Materials (AREA)
  • Glass Compositions (AREA)
  • Ceramic Capacitors (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
  • Photovoltaic Devices (AREA)
  • Non-Insulated Conductors (AREA)
  • Gas-Filled Discharge Tubes (AREA)

Abstract

Cette composition de verre pour une électrode est caractérisée en ce qu'elle contient de l'argent, du phosphore et de l'oxygène, et en ce qu'elle ne contient sensiblement pas de plomb et de bismuth. De préférence, la composition de verre pour une électrode contient du vanadium et du tellure. De façon davantage préférée, la composition de verre contient au moins un élément métal choisi parmi le baryum, le tungstène, le molybdène, le fer, le manganèse et le zinc. En conséquence, il est possible de proposer une composition de verre pour une électrode d'Ag, d'Al ou de Cu formée sur des composants électroniques et une pâte d'électrode utilisant la composition de verre sus-mentionnée, la composition de verre étant une composition de verre qui ne contient sensiblement pas de plomb et de bismuth, lesquels sont nocifs, et qui n'amène pas les propriétés des composants électroniques à se détériorer.
PCT/JP2011/067881 2010-08-11 2011-08-04 Composition de verre pour électrode, pâte pour électrode utilisant ladite composition de verre, et composant électronique utilisant ladite pâte WO2012020694A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2012528656A JP5826178B2 (ja) 2010-08-11 2011-08-04 電極用ガラス組成物、及びそれを用いた電極用ペースト、並びにそれを適用した電子部品
CN201180037099.7A CN103052605B (zh) 2010-08-11 2011-08-04 电极用玻璃组合物、使用该组合物的电极膏、以及使用该电极膏的电子部件
KR1020137000407A KR101414091B1 (ko) 2010-08-11 2011-08-04 전극용 글래스 조성물, 및 그것을 이용한 전극용 페이스트, 및 그것을 적용한 전자 부품

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010179919 2010-08-11
JP2010-179919 2010-08-11

Publications (1)

Publication Number Publication Date
WO2012020694A1 true WO2012020694A1 (fr) 2012-02-16

Family

ID=45567663

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/067881 WO2012020694A1 (fr) 2010-08-11 2011-08-04 Composition de verre pour électrode, pâte pour électrode utilisant ladite composition de verre, et composant électronique utilisant ladite pâte

Country Status (5)

Country Link
JP (1) JP5826178B2 (fr)
KR (1) KR101414091B1 (fr)
CN (1) CN103052605B (fr)
TW (1) TWI448444B (fr)
WO (1) WO2012020694A1 (fr)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012106891A (ja) * 2010-11-18 2012-06-07 Asahi Glass Co Ltd 封着用無鉛ガラス、封着材料、封着材料ペースト
KR20130117344A (ko) * 2012-04-17 2013-10-25 헤레우스 프레셔스 메탈즈 노스 아메리카 콘쇼호켄 엘엘씨 태양 전지 접촉용 전도성 후막 페이스트
JP2014029832A (ja) * 2012-04-17 2014-02-13 Heraeus Precious Metals North America Conshohocken Llc 電気伝導性ペースト組成物用の無機反応系
US8691119B2 (en) 2011-08-11 2014-04-08 E I Du Pont De Nemours And Company Thick film paste containing lead-tellurium-lithium-titanium-oxide and its use in the manufacture of semiconductor devices
WO2014119579A1 (fr) * 2013-02-01 2014-08-07 ナミックス株式会社 Fritte de verre
KR20140123204A (ko) * 2013-04-11 2014-10-22 제일모직주식회사 태양전지 전극 형성용 조성물 및 이로부터 제조된 전극
JP2015109299A (ja) * 2013-12-03 2015-06-11 株式会社ノリタケカンパニーリミテド 放熱性基板
EP2808366A4 (fr) * 2012-01-26 2015-07-15 Hitachi Ind Equipment Sys Encre, base à imprimer, imprimante, procédé d'impression et procédé de production d'une base à imprimer
JPWO2013129578A1 (ja) * 2012-02-28 2015-07-30 京セラ株式会社 太陽電池の電極用導電性ペースト、太陽電池および太陽電池の製造方法
US9196563B2 (en) 2012-01-26 2015-11-24 Hitachi, Ltd. Bonded body and semiconductor module
US20150371728A1 (en) * 2014-06-24 2015-12-24 Samsung Electro-Mechanics Co., Ltd. Multilayer electronic component and conductive paste composition for internal electrode
WO2016017240A1 (fr) * 2014-07-28 2016-02-04 株式会社村田製作所 Pâte conductrice et article de verre
WO2016043095A1 (fr) * 2014-09-19 2016-03-24 株式会社日立製作所 Structure de dissipation thermique et module semi-conducteur l'utilisant
CN105474408A (zh) * 2013-08-30 2016-04-06 京瓷株式会社 太阳能电池元件及其制造方法
WO2016157631A1 (fr) * 2015-03-31 2016-10-06 株式会社日立製作所 Composition de matériau composite et matériau en pâte le comprenant
EP2960936A4 (fr) * 2013-02-22 2016-10-19 Hitachi Ltd Dispositif de commande électronique moulé dans la résine
JPWO2014102915A1 (ja) * 2012-12-26 2017-01-12 株式会社日立製作所 低融点ガラス樹脂複合材料と、それを用いた電子・電気機器、アキシャルギャップモータ
JP2017505977A (ja) * 2014-01-17 2017-02-23 ナミックス株式会社 導電性ペースト及びそれを用いた半導体装置の製造方法
JP6246877B1 (ja) * 2016-09-08 2017-12-13 Ｄｏｗａエレクトロニクス株式会社 導電性ペーストおよびその製造方法、ならびに太陽電池の製造方法
TWI635514B (zh) * 2016-03-18 2018-09-11 大州電子材料股份有限公司 用於太陽能電池之無鉛導電糊料
CN112262112A (zh) * 2018-07-13 2021-01-22 日本电气硝子株式会社 密封材料
WO2021166568A1 (fr) * 2020-02-18 2021-08-26 日本電気硝子株式会社 Composition verrière et produit d'étanchéité
JP2022188286A (ja) * 2017-07-19 2022-12-20 太陽誘電株式会社 積層セラミックコンデンサおよびその製造方法

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI493729B (zh) * 2013-02-08 2015-07-21 Giga Solar Materials Corp 用於太陽能電池正面電極之導電漿及其製造方法
KR101590227B1 (ko) * 2013-06-05 2016-01-29 제일모직주식회사 태양전지 전극　형성용 조성물 및 이로부터 제조된 전극
JP5687369B1 (ja) * 2014-01-29 2015-03-18 保雄 寺谷 空気清浄機
KR101696985B1 (ko) 2014-12-30 2017-01-17 삼성에스디아이 주식회사 태양전지 전극　형성용 조성물 및 이로부터 제조된 전극
JP6336139B2 (ja) * 2015-02-02 2018-06-06 京セラ株式会社 太陽電池素子およびその製造方法
CN107633894A (zh) * 2016-07-19 2018-01-26 翌骅实业股份有限公司 具改质金属粒子的导电胶及其制造方法及太阳能电池组件
DE102017111942A1 (de) * 2017-05-31 2018-12-06 Epcos Ag Hybride Energieversorgungsschaltung, Verwendung einer hybriden Energieversorgungsschaltung und Verfahren zur Herstellung einer hybriden Energieversorgungsschaltung
KR102122607B1 (ko) * 2018-06-22 2020-06-12 에어티앤에스 주식회사 Arche glass를 이용한 태양전지 전극용 페이스트 조성물 및 이를 사용한 태양전지
KR102671969B1 (ko) * 2019-08-16 2024-06-05 삼성전기주식회사 적층형 커패시터 및 그 실장 기판

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59162147A (ja) * 1983-03-03 1984-09-13 Takeshi Nomura ガラス
JPH08502468A (ja) * 1992-10-19 1996-03-19 ディーマット・インコーポレイテッド 改良された熱応力特性を有する低温ガラスおよびその使用方法
JPH11349347A (ja) * 1998-06-08 1999-12-21 Asahi Glass Co Ltd 結晶性低融点ガラス組成物
JP2000265144A (ja) * 1999-03-16 2000-09-26 Sumitomo Bakelite Co Ltd ダイアタッチペースト
JP2002026037A (ja) * 2000-07-05 2002-01-25 Shinko Electric Ind Co Ltd 配線基板及び半導体装置
JP2009209032A (ja) * 2008-02-08 2009-09-17 Hitachi Powdered Metals Co Ltd ガラス組成物

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4945071A (en) * 1989-04-19 1990-07-31 National Starch And Chemical Investment Holding Company Low softening point metallic oxide glasses suitable for use in electronic applications
US5076876A (en) * 1989-06-21 1991-12-31 Diemat, Inc. Method of attaching an electronic device to a substrate
JPH06121800A (ja) * 1992-10-08 1994-05-06 Olympus Optical Co Ltd 歯科補綴物の製造方法
US6322620B1 (en) * 2000-11-16 2001-11-27 National Starch And Chemical Investment Holding Corporation Conductive ink composition
US8093491B2 (en) * 2005-06-03 2012-01-10 Ferro Corporation Lead free solar cell contacts

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59162147A (ja) * 1983-03-03 1984-09-13 Takeshi Nomura ガラス
JPH08502468A (ja) * 1992-10-19 1996-03-19 ディーマット・インコーポレイテッド 改良された熱応力特性を有する低温ガラスおよびその使用方法
JPH11349347A (ja) * 1998-06-08 1999-12-21 Asahi Glass Co Ltd 結晶性低融点ガラス組成物
JP2000265144A (ja) * 1999-03-16 2000-09-26 Sumitomo Bakelite Co Ltd ダイアタッチペースト
JP2002026037A (ja) * 2000-07-05 2002-01-25 Shinko Electric Ind Co Ltd 配線基板及び半導体装置
JP2009209032A (ja) * 2008-02-08 2009-09-17 Hitachi Powdered Metals Co Ltd ガラス組成物

Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012106891A (ja) * 2010-11-18 2012-06-07 Asahi Glass Co Ltd 封着用無鉛ガラス、封着材料、封着材料ペースト
US8691119B2 (en) 2011-08-11 2014-04-08 E I Du Pont De Nemours And Company Thick film paste containing lead-tellurium-lithium-titanium-oxide and its use in the manufacture of semiconductor devices
US9196563B2 (en) 2012-01-26 2015-11-24 Hitachi, Ltd. Bonded body and semiconductor module
EP2808366A4 (fr) * 2012-01-26 2015-07-15 Hitachi Ind Equipment Sys Encre, base à imprimer, imprimante, procédé d'impression et procédé de production d'une base à imprimer
US9334415B2 (en) 2012-01-26 2016-05-10 Hitachi Industrial Equipment Systems Co., Ltd. Ink, base to be printed, printing device, printing method, and method for producing base to be printed
JPWO2013129578A1 (ja) * 2012-02-28 2015-07-30 京セラ株式会社 太陽電池の電極用導電性ペースト、太陽電池および太陽電池の製造方法
KR20130117344A (ko) * 2012-04-17 2013-10-25 헤레우스 프레셔스 메탈즈 노스 아메리카 콘쇼호켄 엘엘씨 태양 전지 접촉용 전도성 후막 페이스트
JP2014029832A (ja) * 2012-04-17 2014-02-13 Heraeus Precious Metals North America Conshohocken Llc 電気伝導性ペースト組成物用の無機反応系
KR101908738B1 (ko) 2012-04-17 2018-10-16 헤레우스 프레셔스 메탈즈 노스 아메리카 콘쇼호켄 엘엘씨 태양 전지 접촉용 전도성 후막 페이스트
JPWO2014102915A1 (ja) * 2012-12-26 2017-01-12 株式会社日立製作所 低融点ガラス樹脂複合材料と、それを用いた電子・電気機器、アキシャルギャップモータ
JPWO2014119579A1 (ja) * 2013-02-01 2017-01-26 ナミックス株式会社 ガラスフリット
US9776909B2 (en) 2013-02-01 2017-10-03 Namics Corporation Glass frit
CN105073672B (zh) * 2013-02-01 2019-04-12 纳美仕有限公司 玻璃料
CN105073672A (zh) * 2013-02-01 2015-11-18 纳美仕有限公司 玻璃料
WO2014119579A1 (fr) * 2013-02-01 2014-08-07 ナミックス株式会社 Fritte de verre
EP2960936A4 (fr) * 2013-02-22 2016-10-19 Hitachi Ltd Dispositif de commande électronique moulé dans la résine
KR20140123204A (ko) * 2013-04-11 2014-10-22 제일모직주식회사 태양전지 전극 형성용 조성물 및 이로부터 제조된 전극
US9608136B2 (en) 2013-04-11 2017-03-28 Samsung Sdi Co., Ltd. Composition for solar cell electrodes and electrode fabricated using the same
KR101882525B1 (ko) * 2013-04-11 2018-07-26 삼성에스디아이 주식회사 태양전지 전극 형성용 조성물 및 이로부터 제조된 전극
US9608137B2 (en) 2013-04-11 2017-03-28 Samsung Sdi Co., Ltd. Composition for solar cell electrodes and electrode fabricated using the same
CN105474408A (zh) * 2013-08-30 2016-04-06 京瓷株式会社 太阳能电池元件及其制造方法
JP2015109299A (ja) * 2013-12-03 2015-06-11 株式会社ノリタケカンパニーリミテド 放熱性基板
JP2017505977A (ja) * 2014-01-17 2017-02-23 ナミックス株式会社 導電性ペースト及びそれを用いた半導体装置の製造方法
US9576697B2 (en) * 2014-06-24 2017-02-21 Samsung Electro-Mechanics Co., Ltd. Multilayer electronic component and conductive paste composition for internal electrode
US20150371728A1 (en) * 2014-06-24 2015-12-24 Samsung Electro-Mechanics Co., Ltd. Multilayer electronic component and conductive paste composition for internal electrode
JP2016009861A (ja) * 2014-06-24 2016-01-18 サムソン エレクトロ−メカニックス カンパニーリミテッド． 積層電子部品及び内部電極用導電性ペースト組成物
US9824791B2 (en) 2014-06-24 2017-11-21 Samsung Electro-Mechanics Co., Ltd. Multilayer electronic component and conductive paste composition for internal electrode
WO2016017240A1 (fr) * 2014-07-28 2016-02-04 株式会社村田製作所 Pâte conductrice et article de verre
JPWO2016043095A1 (ja) * 2014-09-19 2017-05-25 株式会社日立製作所 放熱構造体及びそれを利用した半導体モジュール
US10177069B2 (en) 2014-09-19 2019-01-08 Hitachi Ltd. Heat-dissipating structure and semiconductor module using same
WO2016043095A1 (fr) * 2014-09-19 2016-03-24 株式会社日立製作所 Structure de dissipation thermique et module semi-conducteur l'utilisant
WO2016157631A1 (fr) * 2015-03-31 2016-10-06 株式会社日立製作所 Composition de matériau composite et matériau en pâte le comprenant
TWI635514B (zh) * 2016-03-18 2018-09-11 大州電子材料股份有限公司 用於太陽能電池之無鉛導電糊料
WO2018047822A1 (fr) * 2016-09-08 2018-03-15 Ｄｏｗａエレクトロニクス株式会社 Pâte conductrice, son procédé de production, et procédé de production de cellule solaire
JP2018041663A (ja) * 2016-09-08 2018-03-15 Ｄｏｗａエレクトロニクス株式会社 導電性ペーストおよびその製造方法、ならびに太陽電池の製造方法
JP6246877B1 (ja) * 2016-09-08 2017-12-13 Ｄｏｗａエレクトロニクス株式会社 導電性ペーストおよびその製造方法、ならびに太陽電池の製造方法
US10833209B2 (en) 2016-09-08 2020-11-10 Dowa Electronics Materials Co., Ltd. Conductive paste, method for producing same, and method for producing solar cell
JP2022188286A (ja) * 2017-07-19 2022-12-20 太陽誘電株式会社 積層セラミックコンデンサおよびその製造方法
CN112262112A (zh) * 2018-07-13 2021-01-22 日本电气硝子株式会社 密封材料
CN112262112B (zh) * 2018-07-13 2023-03-28 日本电气硝子株式会社 密封材料
WO2021166568A1 (fr) * 2020-02-18 2021-08-26 日本電気硝子株式会社 Composition verrière et produit d'étanchéité

Also Published As

Publication number Publication date
JPWO2012020694A1 (ja) 2013-10-28
KR20130041076A (ko) 2013-04-24
TW201213268A (en) 2012-04-01
TWI448444B (zh) 2014-08-11
CN103052605A (zh) 2013-04-17
CN103052605B (zh) 2016-01-20
JP5826178B2 (ja) 2015-12-02
KR101414091B1 (ko) 2014-07-02

Similar Documents

Publication Publication Date Title
JP5826178B2 (ja) 電極用ガラス組成物、及びそれを用いた電極用ペースト、並びにそれを適用した電子部品
JP5215458B2 (ja) 導電性ペースト及びそれを用いた電極配線を具備する電子部品
JP5699933B2 (ja) ガラス組成物およびそれを用いた導電性ペースト組成物、電極配線部材と電子部品
JP5497504B2 (ja) 電子部品
JP5414409B2 (ja) 低融点ガラス組成物、それを用いた低温封着材料及び電子部品
TWI478890B (zh) An electronic component, a conductive paste for an aluminum electrode thereof, and a glass composition for an aluminum electrode
JP5416631B2 (ja) アルミニウム電極配線用のガラス組成物と導電性ペースト、そのアルミニウム電極配線を具備する電子部品、及び、この電子部品の製造方法
JP5494619B2 (ja) 電子部品、それに適用されるアルミニウム電極用導電性ペースト、及びアルミニウム電極用ガラス組成物
JP5747096B2 (ja) 導電性ペースト
JP5546074B2 (ja) 導電性ペースト及びそれを用いた電極配線を具備する電子部品

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180037099.7

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11816360

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012528656

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 20137000407

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11816360

Country of ref document: EP

Kind code of ref document: A1