WO2010137667A1 - Élément de verre avec une couche de matériau d'étanchéité attachée à celui-ci, dispositif électronique obtenu à l'aide de celui-ci et son procédé de fabrication - Google Patents

Élément de verre avec une couche de matériau d'étanchéité attachée à celui-ci, dispositif électronique obtenu à l'aide de celui-ci et son procédé de fabrication Download PDF

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Publication number
WO2010137667A1
WO2010137667A1 PCT/JP2010/059043 JP2010059043W WO2010137667A1 WO 2010137667 A1 WO2010137667 A1 WO 2010137667A1 JP 2010059043 W JP2010059043 W JP 2010059043W WO 2010137667 A1 WO2010137667 A1 WO 2010137667A1
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WIPO (PCT)
Prior art keywords
glass
sealing
glass substrate
material layer
thermal expansion
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PCT/JP2010/059043
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English (en)
Japanese (ja)
Inventor
幸一 渋谷
旭 井出
壮平 川浪
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旭硝子株式会社
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Priority to JP2011516062A priority Critical patent/JPWO2010137667A1/ja
Publication of WO2010137667A1 publication Critical patent/WO2010137667A1/fr

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    • 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
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • 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
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
    • 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
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • 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
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • 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
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants

Definitions

  • the present invention relates to a glass member with a sealing material layer, an electronic device using the same, and a method for producing the same.
  • a solar cell such as a dye-sensitized solar cell
  • a battery element photoelectric conversion element
  • two glass substrates see Patent Document 1.
  • FPD flat panel display device
  • OELD organic Electro-Luminescence Display
  • PDP plasma display panel
  • LCD liquid crystal display device
  • sealing glass excellent in moisture resistance and the like is being promoted as a sealing material for sealing between two glass substrates. Since the sealing temperature with the sealing glass is about 400 to 600 ° C., the characteristics of the electronic element parts such as the dye-sensitized solar cell element and the OEL element containing the electrolyte deteriorate when fired in a heating furnace. End up. Therefore, a sealing material layer including a laser absorbing material is disposed between the sealing regions provided in the peripheral portions of the two glass substrates, and the sealing layer is formed by irradiating the laser beam to this and heating and melting it. Attempts have been made (see Patent Documents 1 to 3).
  • Laser sealing can suppress the thermal influence on the electronic element part, but it is difficult to crack or break the glass substrate and peel off the conductive film formed on the surface of the glass substrate.
  • a sealing glass material including a laser absorbing material is baked on a sealing region of one glass substrate to form a frame-shaped sealing material layer.
  • the laser material is irradiated from one glass substrate side, and the sealing material layer is heated and melted.
  • the electronic element part provided between the glass substrates is sealed.
  • Patent Document 1 describes a sealing glass material having a difference in thermal expansion coefficient of 10 ⁇ 10 ⁇ 7 / ° C. or less from a glass substrate and a glass panel using the same.
  • a transparent conductive film is formed on the surface of the glass substrate as a wiring layer or the like for drawing out the electrode of the electronic element part to the outside of the glass panel.
  • Glass materials for sealing that reduce the difference in thermal expansion coefficient with conventional glass substrates are effective for suppressing cracks and cracks in the glass substrate during laser irradiation, and peeling between the glass substrate and the sealing layer.
  • the transparent conductive film on the surface of the substrate is easily peeled off after laser sealing, thereby impairing the airtightness of the glass panel.
  • FTO fluorine-doped tin oxide
  • the object of the present invention is to prevent the occurrence of defects such as cracks and cracks in a glass substrate made of soda lime glass when applying laser sealing to the sealing between two glass substrates, and a transparent conductive film (FTO film). )
  • FTO film transparent conductive film
  • a glass member with a sealing material layer has a surface provided with a sealing region, and is formed on a glass substrate made of soda lime glass and the sealing region of the glass substrate, and is a sealing glass. And a sealing material layer with a sealing material layer comprising a fired layer of a sealing glass material containing a low expansion filler and a laser absorbing material, wherein the sealing region of the glass substrate A transparent conductive film made of fluorine-doped tin oxide is formed on the surface of the sealing material layer, and the thermal expansion coefficient ⁇ 1 of the sealing material layer is determined by the value of the thermal expansion coefficient ⁇ 2 of the transparent conductive film and the heat of the glass substrate.
  • One of 0.5 times the value of the expansion coefficient ⁇ 3 whichever is greater, and two times the thermal expansion coefficient ⁇ 2 of the transparent conductive film and the value of the thermal expansion coefficient ⁇ 3 of the glass substrate It is characterized by being less than a small value.
  • An electronic device includes a first glass substrate having a surface including a first sealing region, and a surface including a second sealing region corresponding to the first sealing region.
  • a second glass substrate disposed so that the surface faces the surface of the first glass substrate, and an electronic device provided between the first glass substrate and the second glass substrate Part and the first sealing region of the first glass substrate and the second sealing region of the second glass substrate so as to seal the electronic element part,
  • a sealing layer made of a fused and fixed layer of a sealing glass material containing a sealing glass, a low expansion filler, and a laser absorbing material, wherein the first and second glass substrates are made of soda lime glass.
  • the table including the first sealing region of the first glass substrate.
  • a fluorine-doped transparent conductive film made of tin oxide is formed, the thermal expansion coefficient of the sealing layer alpha 1 , said either larger value than the transparent conductive 0.5 times the value of the thermal expansion coefficient alpha 2 value and the thermal expansion coefficient alpha 3 of the glass substrate layer, and the thermal expansion coefficient of the transparent conductive film alpha 2 is characterized in that the at most one small value twice the value and the value of the thermal expansion coefficient alpha 3 of the glass substrate.
  • the manufacturing method of the electronic device which concerns on the aspect of this invention has the surface provided with a 1st sealing area
  • a second glass substrate made of soda lime glass having a surface with a second sealing region, the first sealing region of the first glass substrate, or of the second glass substrate; Forming a sealing material layer composed of a fired layer of a sealing glass material containing a sealing glass, a low expansion filler, and a laser absorbing material in the second sealing region;
  • the first glass substrate and the second glass substrate are laminated through the sealing material layer while facing the surface and the surface of the second glass substrate, and then the first glass substrate.
  • a method for manufacturing an electronic device comprising: the surface including the first sealing region of the first glass substrate; and the second sealing region of the second glass substrate.
  • a transparent conductive film made of fluorine-doped tin oxide is formed on at least one of the surfaces, and the thermal expansion coefficient ⁇ 1 of the sealing material layer is equal to the value of the thermal expansion coefficient ⁇ 2 of the transparent conductive film and the glass substrate.
  • thermal expansion coefficient ⁇ 3 of the glass substrate whichever is greater than 0.5 times, which is greater than the value of the thermal expansion coefficient ⁇ 2 of the transparent conductive film and the thermal expansion coefficient ⁇ 3 of the glass substrate. It is characterized by being any smaller value.
  • the electronic device using the same, and the manufacturing method thereof, the occurrence of defects such as cracks and cracks in the glass substrate made of soda lime glass at the time of laser sealing. While preventing, the crack of a transparent conductive film (FTO film
  • membrane transparent conductive film
  • FIG. 5 is a cross-sectional view taken along line AA in FIG. 4.
  • FIG. 7 is a cross-sectional view taken along line AA in FIG. 6.
  • FIG. 3 is an enlarged cross-sectional view showing a part of the manufacturing process of the electronic device shown in FIG. 2. It is sectional drawing which expands and shows a part of electronic device shown in FIG.
  • FIG. 1 is a diagram showing an electronic device according to an embodiment of the present invention
  • FIG. 2 is a diagram showing a configuration example of an electronic element part in the electronic device shown in FIG. 1
  • FIG. 3 is a process for manufacturing an electronic device according to an embodiment of the present invention.
  • FIGS. 4 to 7 are diagrams showing configurations of the first and second glass substrates used therefor
  • FIG. 8 is an enlarged view showing a part of the manufacturing process of the electronic device
  • FIG. 9 is a view of sealing the electronic device. It is a figure which expands and shows a wearing part.
  • the electronic device 1 shown in FIG. 1 constitutes a solar cell such as a dye-sensitized solar cell, or a lighting device (OEL illumination or the like) using a light emitting element such as an OPD, PDP, LCD, or other FPD, or OEL element.
  • the electronic device 1 includes a first glass substrate 2 and a second glass substrate 3.
  • the first and second glass substrates 2 and 3 are made of soda lime glass. Various known compositions can be applied to soda lime glass.
  • the soda lime glass constituting the first and second glass substrates 2 and 3 has a thermal expansion coefficient in the range of 80 to 90 ( ⁇ 10 ⁇ 7 / ° C.), for example.
  • An electronic element unit 4 corresponding to the electronic device 1 is provided between the surface 2a of the first glass substrate 2 and the surface 3a of the second glass substrate 3 opposed thereto.
  • the electronic element unit 4 is, for example, a dye-sensitized solar cell element (dye-sensitized photoelectric conversion element) for a solar cell, an OEL element for OELD or OEL illumination, a plasma light-emitting element or an LCD for PDP.
  • the electronic element portion 4 including a solar cell element such as a dye-sensitized solar cell element, a light emitting element such as an OEL element, and the like has various known structures.
  • the electronic device 1 of this embodiment is not limited to the element structure of the electronic element unit 4.
  • FIG. 2 shows an example of the structure of the dye-sensitized solar cell element 40 as a configuration example of the electronic element unit 4.
  • a semiconductor electrode (photoelectrode / anode) 42 having a sensitizing dye is provided on the surface 2 a of the first glass substrate 2 via a transparent conductive film 41.
  • a counter electrode (cathode) 44 is provided on the surface 3 a of the second glass substrate 3 facing the surface 2 a of the first glass substrate 2 via a transparent conductive film 43.
  • the transparent conductive films 41 and 43 are made of a fluorine-doped tin oxide (FTO) film.
  • the semiconductor electrode 42 is made of a metal oxide such as titanium oxide, zirconium oxide, niobium oxide, tantalum oxide, tin oxide, or zinc oxide.
  • the semiconductor electrode 42 is composed of a metal oxide porous film, and a sensitizing dye is adsorbed therein. Examples of the sensitizing dye include metal complex dyes such as ruthenium complex dyes and osmium complex dyes, and organic dyes such as cyanine dyes, merocyanine dyes, and triphenylmethane dyes.
  • the counter electrode 44 is made of a thin film such as platinum, gold, or silver.
  • An electrolyte 45 is enclosed between the first glass substrate 2 and the second glass substrate 3, and the dye-sensitized solar cell element 40 is configured by these components.
  • element films such as wiring films and electrode films forming an element structure are formed on the surfaces 2a and 3a of the first and second glass substrates 2 and 3, respectively.
  • the configuration of the electronic element unit 4 is not limited to this.
  • the first glass substrate 2 is used as an element glass substrate, and an element structure is formed on the surface thereof.
  • the second glass substrate 3 is used as a sealing member (sealing glass substrate) for the OEL element formed on the surface of the first glass substrate 2.
  • the element film constituting the electronic element unit 4 and the element structure based thereon are formed on at least one of the surfaces 2 a and 3 a of the first and second glass substrates 2 and 3.
  • a first sealing region 2B is provided along the outer periphery of the region 2A.
  • the first sealing region 2B is provided so as to surround the first element formation region 2A.
  • the surface 3a of the second glass substrate 3 corresponds to the second element forming region 3A corresponding to the first element forming region 2A and the first sealing region 2B.
  • a second sealing region 3B is provided.
  • the electronic element portion 4 is formed in the second element formation region 3A.
  • Part (4B) is formed.
  • the first glass substrate 2 is used as a glass substrate for an element such as a light emitting element such as an OEL element
  • the second element formation region 3A on the surface 3a of the second glass substrate 3 is the first element formation region. It becomes a region opposite to 2A.
  • the first and second sealing regions 2B and 3B are sealing layer formation regions (sealing material layer formation regions for the second sealing region 3B).
  • the first glass substrate 2 and the second glass substrate 3 are arranged with a predetermined gap so that the surfaces 2a and 3a on which the structures 4A and 4B of the electronic element unit 4 are formed face each other.
  • a gap between the first glass substrate 2 and the second glass substrate 3 is sealed with a sealing layer 5. That is, the sealing layer 5 is formed between the sealing region 2B of the first glass substrate 2 and the sealing region 3B of the second glass substrate 3 so as to seal the electronic element portion 4.
  • the electronic element unit 4 is hermetically sealed with a glass panel including a first glass substrate 2, a second glass substrate 3, and a sealing layer 5.
  • the sealing layer 5 has a thickness in the range of 10 to 100 ⁇ m, for example.
  • the electronic element unit 4 When the dye-sensitized solar cell element 40 or the like is applied as the electronic element unit 4, the electronic element unit 4 is disposed in the entire gap between the first glass substrate 2 and the second glass substrate 3. Further, when an OEL element or the like is applied as the electronic element unit 4, a partial space remains between the first glass substrate 2 and the second glass substrate 3. Such a space may be left as it is, or may be filled with a transparent resin or the like. The transparent resin may be adhered to the glass substrates 2 and 3 or may simply be in contact with the glass substrates 2 and 3.
  • the sealing layer 5 is a melt-fixed layer in which the sealing material layer 6 formed in the sealing region 3B of the second glass substrate 3 is melted with a laser beam and fixed to the sealing region 2B of the first glass substrate 2. It consists of That is, a frame-shaped sealing material layer 6 is formed in the sealing region 3B of the second glass substrate 3 used for manufacturing the electronic device 1 as shown in FIGS. By sealing the sealing material layer 6 formed in the sealing region 3B of the second glass substrate 3 to the sealing region 2B of the first glass substrate 2 with the heat of the laser beam, the first glass substrate is obtained. A sealing layer 5 that seals between 2 and the second glass substrate 3 is formed.
  • the sealing material layer 6 is a fired layer of a sealing glass material containing a sealing glass, a low expansion filler, and a laser absorber.
  • the glass material for sealing is obtained by blending a laser absorbing material and a low expansion filler into sealing glass as a main component.
  • the glass material for sealing may contain additives other than these as required.
  • the sealing glass glass frit
  • low melting point glass such as tin-phosphate glass, bismuth glass, vanadium glass, lead glass and the like is used.
  • tin-phosphate glass is used in consideration of sealing properties (adhesiveness) to glass substrates 2 and 3, reliability thereof (adhesion reliability and sealing properties), and influence on the environment and human body. It is preferable to use sealing glass made of bismuth glass.
  • Tin-phosphate glass is composed of 20 to 68 mol% SnO, 0.5 to 5 mol% SnO 2 and 20 to 40 mol% P 2 O 5 (basically a total amount of 100%). It is preferable to have a composition of (mol%). SnO is a component for lowering the melting point of glass. If the SnO content is less than 20 mol%, the viscosity of the glass becomes high and the sealing temperature becomes too high, and if it exceeds 68 mol%, it will not vitrify.
  • SnO 2 is a component for stabilizing the glass.
  • SnO 2 is a component for stabilizing the glass.
  • SnO 2 is separated and precipitated in the glass that has been softened and melted during the sealing operation, the fluidity is impaired, and the sealing workability is lowered.
  • SnO 2 exceeds 5 mol%, SnO 2 is likely to precipitate during melting of the low-melting glass.
  • P 2 O 5 is a component for forming a glass skeleton.
  • the content of P 2 O 5 is less than 20 mol%, the glass does not vitrify, and when the content exceeds 40 mol%, the weather resistance, which is a disadvantage specific to phosphate glass, may be deteriorated.
  • the ratio (mol%) of SnO and SnO 2 in the glass frit can be determined as follows. First, after the glass frit (low melting point glass powder) is acid-decomposed, the total amount of Sn atoms contained in the glass frit is measured by ICP emission spectroscopic analysis. Next, since Sn 2+ (SnO) is obtained by acidimetric decomposition, the amount of Sn 2+ determined there is subtracted from the total amount of Sn atoms to obtain Sn 4+ (SnO 2 ).
  • the glass formed of the above three components has a low glass transition point and is suitable for a low-temperature sealing material.
  • a component that forms a glass skeleton such as SiO 2 , ZnO, B 2 O 3 , Al 2 O 3, WO 3, MoO 3, Nb 2 O 5, TiO 2, ZrO 2, Li 2 O, stabilizing Na 2 O, K 2 O, Cs 2 O, MgO, CaO, SrO, the glass BaO, etc.
  • the component to be made may be contained as an optional component. However, if the content of any component is too large, the glass becomes unstable and devitrification may occur, and the glass transition point and softening point may increase. Therefore, the total content of any component is 30 mol%. The following is preferable.
  • the glass composition in this case is adjusted so that the total amount of the basic component and the optional component is basically 100 mol%.
  • Bismuth-based glass (gas frit) consists of 70 to 90% by mass of Bi 2 O 3 , 1 to 20% by mass of ZnO and 2 to 12% by mass of B 2 O 3 (basically, the total amount is 100% by mass).
  • Bi 2 O 3 is a component that forms a glass network.
  • the content of Bi 2 O 3 is less than 70% by mass, the softening point of the low-melting glass becomes high and sealing at a low temperature becomes difficult.
  • the content of Bi 2 O 3 exceeds 90% by mass, it becomes difficult to vitrify and the thermal expansion coefficient tends to be too high.
  • ZnO is a component that lowers the thermal expansion coefficient and the like. Vitrification becomes difficult when the content of ZnO is less than 1% by mass. When the content of ZnO exceeds 20% by mass, stability during low-melting glass molding is lowered, and devitrification is likely to occur.
  • B 2 O 3 is a component that forms a glass skeleton and widens the range in which vitrification is possible. When the content of B 2 O 3 is less than 2% by mass, vitrification becomes difficult, and when it exceeds 12% by mass, the softening point becomes too high, and even if a load is applied during sealing, sealing is performed at a low temperature. It becomes difficult.
  • the glass formed of the above three components has a low glass transition point and is suitable for a low-temperature sealing material, but Al 2 O 3 , CeO 2 , SiO 2 , Ag 2 O, MoO 3 , Nb 2 O 5, Ta 2 O 5, Ga 2 O 3, Sb 2 O 3, Li 2 O, Na 2 O, K 2 O, Cs 2 O, CaO, SrO, BaO, WO 3, P 2 O 5, SnO x (X is 1 or 2) etc. may be contained. However, if the content of any component is too large, the glass becomes unstable and devitrification may occur, and the glass transition point and softening point may increase. Therefore, the total content of any component is 30% by mass. The following is preferable.
  • the glass composition in this case is adjusted so that the total amount of the basic component and the optional component is basically 100% by mass.
  • the glass material for sealing contains a low expansion filler.
  • a low expansion filler it is preferable to use at least one selected from silica, alumina, zirconia, zirconium silicate, cordierite, zirconium phosphate compound, soda lime glass, and borosilicate glass.
  • Zirconium phosphate compounds include (ZrO) 2 P 2 O 7 , NaZr 2 (PO 4 ) 3 , KZr 2 (PO 4 ) 3 , Ca 0.5 Zr 2 (PO 4 ) 3 , Na 0.5 Nb.
  • the low expansion filler has a lower thermal expansion coefficient than the sealing glass which is the main component of the sealing glass material.
  • the content of the low expansion filler is appropriately set so that the thermal expansion coefficient of the sealing glass approaches the thermal expansion coefficient of the glass substrates 2 and 3.
  • the low expansion filler is preferably contained in the range of 20 to 50% by volume with respect to the sealing glass material, although it depends on the thermal expansion coefficient of the sealing glass and the glass substrates 2 and 3. If the content of the low expansion filler is less than 20% by volume, the effect of adjusting the thermal expansion coefficient of the glass material for sealing cannot be sufficiently obtained.
  • content of a low expansion filler exceeds 50 volume%, there exists a possibility that the fluidity
  • the glass material for sealing further contains a laser absorber.
  • a laser absorber As the laser absorbing material, a compound such as at least one metal selected from Fe, Cr, Mn, Co, Ni and Cu or an oxide containing the metal is used.
  • the content of the laser absorber is preferably in the range of 0.1 to 10% by volume with respect to the sealing glass material. When the content of the laser absorber is less than 0.1% by volume, the sealing material layer 6 cannot be sufficiently melted at the time of laser irradiation. If the content of the laser absorber exceeds 10% by volume, the second glass substrate 3 may be cracked due to local heat generation in the vicinity of the interface with the second glass substrate 3 during laser irradiation. There is a possibility that the fluidity at the time of melting of the wearing glass material is deteriorated and the adhesiveness with the first glass substrate 2 is lowered.
  • transparent conductive films 7 and 8 made of an FTO film are formed as shown in FIG.
  • the FTO film is formed by a PVD method such as a sputtering method or a laser ablation method, a CVD method, a spray pyrolysis method or the like, and has a film thickness in the range of, for example, 0.1 to 1 ⁇ m.
  • the transparent conductive films 7 and 8 made of such an FTO film function as at least a part of the wiring for drawing out the electrode of the electronic element unit 4 to the outside of the glass panel, and are formed so as to cross the sealing regions 2B and 3B, respectively. Is done. Therefore, as shown in FIG.
  • the wiring may be pulled out from only one side of the electronic element part 4.
  • the transparent conductive film formed on one of the surfaces 2 a and 3 a of the first and second glass substrates 2 is in contact with the sealing material layer 6 and the sealing layer 5.
  • the transparent conductive film 7 generally formed on the surface 2 a of the first glass substrate 2 is formed with the sealing material layer 6 and the sealing layer 5. Will be in touch.
  • the transparent conductive film is formed on the surfaces 2 a and 3 a including at least one of the sealing regions 2 ⁇ / b> B and 3 ⁇ / b> B of the first and second glass substrates 2.
  • the sealing material layer 6 When the sealing material layer 6 is irradiated with a laser beam and melted, the sealing material layer 6 is melted in order from a portion irradiated with the laser beam scanned along the sealing material layer 6 and rapidly cooled and solidified upon completion of the laser beam irradiation. It adheres to the first glass substrate 2.
  • stress is applied to the transparent conductive films 7 and 8 based on the difference in thermal expansion with the glass substrates 2 and 3 and the difference in thermal expansion with the sealing material layer 6.
  • the thermal expansion coefficient of soda lime glass constituting the glass substrates 2 and 3 is 80 to 90 ⁇ 10 ⁇ 7 / ° C.
  • the thermal expansion coefficient of the FTO constituting the transparent conductive films 7 and 8 is representative. Specifically, it is 38 ⁇ 10 ⁇ 7 / ° C.
  • the thermal expansion coefficient of the FTO film is also equivalent.
  • the thermal expansion coefficients of the transparent conductive films 7 and 8 are smaller than those of the glass substrates (soda lime glass) 2 and 3, the transparent conductive film 7 is heated when the sealing material layer 6 is heated and melted. , 8 and the glass substrates 2 and 3 are stressed, but do not lead to mutual destruction or peeling of the transparent conductive films 7 and 8. Further, since the sealing material layer 6 is softened and fluidized, no stress is generated between the transparent conductive films 7 and 8 and the sealing material layer 6. In the process in which the irradiation of the laser beam is completed and the sealing material layer 6 is cooled, the glass substrates 2 and 3, the transparent conductive films 7 and 8, and the sealing material layer 6 contract.
  • the sealing material layer 6 has a thermal expansion coefficient similar to that of the glass substrates 2 and 3, the glass substrates 2 and 3, the sealing material layer 6, the transparent conductive films 7 and 8, Since the shrinkage amount of the glass substrates 2, 3 and the sealing material layer 6 is larger than the shrinkage amount of the transparent conductive films 7, 8 based on the difference in thermal expansion between the transparent conductive films 7, 8, strong compressive stress is applied to the transparent conductive films 7, 8. Will occur. In particular, the stress increases when the thickness of the sealing layer 5 is 10 times or more the thickness of the transparent conductive films 7 and 8.
  • the transparent conductive films 7 and 8 Since the stress applied to the transparent conductive films 7 and 8 is different between a portion where the sealing material layer 6 is formed and a portion where the sealing material layer 6 is not formed, the transparent conductive films 7 and 8 have a region where the sealing material layer 6 is formed. Along the surface of the transparent conductive films 7 and 8 and the glass substrates 2 and 3.
  • the FTO film constituting the transparent conductive films 7 and 8 is mainly composed of an aggregate (polycrystal) of tin oxide crystal grains, and fluorine and tin oxide containing fluorine exist at the grain boundaries of such crystal grains. It has a form. Since the grain boundary in the FTO film scatters light, it contributes to uniform light irradiation, uniform radiation, and the like, but it is a factor of decreasing the mechanical strength of the FTO film. That is, the FTO film is likely to crack along the grain boundaries inside. For this reason, when an FTO film is applied to the transparent conductive films 7 and 8, the transparent conductive film 7 is based on the difference in thermal expansion between the glass substrates 2 and 3 and the sealing material layer 6 and the transparent conductive films 7 and 8. , 8 are likely to cause cracks and peeling due to grain boundary cracks.
  • the sealing material layer 6 has a thermal expansion coefficient similar to that of the transparent conductive films (FTO films) 7 and 8, the glass substrates 2 and 3, the sealing material layer 6, and the transparent conductive film
  • the sealing material layer 6 and the transparent conductive films 7 and 8 both apply tensile stress to the glass substrates 2 and 3 based on the difference in thermal expansion with respect to 7 and 8.
  • the FTO film is a non-uniform layer having crystal grain boundaries as described above, the stress of the sealing material layer 6 is transmitted to the glass substrates 2 and 3 through the grain boundaries, and the glass substrates 2 and 3 and the transparent conductive film 7. , 8 is increased in stress at the interface. For this reason, the transparent conductive films 7 and 8 are easily cracked along the region where the sealing material layer 6 is formed, and further, peeling occurs at the interface between the transparent conductive films 7 and 8 and the glass substrates 2 and 3.
  • the first glass substrate 2 is likely to be cracked or broken.
  • the difference in thermal expansion between the glass substrates 2 and 3 and the sealing material layer 6 is large, the stress applied to the glass substrates 2 and 3 increases regardless of the presence or absence of the transparent conductive films 7 and 8. The first and second glass substrates 2 and 3 are likely to crack and break.
  • the thermal expansion coefficient ⁇ 1 of the sealing material layer 6 is set to the value of the thermal expansion coefficient ⁇ 2 of the transparent conductive films (FTO films) 7 and 8 ( ⁇ 2 value). in any large value over 0.5 times the value of the thermal expansion coefficient alpha 3 of the glass substrate 2,3 (0.5 ⁇ 3 value), and a transparent conductive film (FTO film) thermal expansion coefficient of 7, 8 alpha 2 It is adjusted to one smaller the range of 2 times the value (2.alpha 2 values) and the thermal expansion coefficient alpha 3 of the value of the glass substrate 2,3 (alpha 3 value).
  • the sealing material layer 6 having such a thermal expansion coefficient ⁇ 1 , and by extension, the sealing layer 5, the glass substrate 2, 3 made of soda lime glass is suppressed from being inconveniences such as cracks and cracks, and the glass substrate. It is possible to suppress peeling of the transparent conductive films (FTO films) 7 and 8 from 2 and 3.
  • the thermal expansion coefficient ⁇ 1 of the sealing material layer 6 exceeds either the 2 ⁇ 2 value or the ⁇ 3 value, the glass substrates 2 and 3 and the sealing material layer are compared with the shrinkage amount of the transparent conductive films 7 and 8. Since the shrinkage amount of 6 increases, a strong compressive stress is generated in the transparent conductive films 7 and 8, and cracks are easily generated in the transparent conductive films 7 and 8 based on this.
  • the thermal expansion coefficient ⁇ 1 of the sealing material layer 6 is less than either ⁇ 2 value or 0.5 ⁇ 3 value, it is added to the interface between the glass substrates 2 and 3 and the transparent conductive films 7 and 8. Stress increases, and cracks are likely to occur in the transparent conductive films 7 and 8 based on the stress.
  • the sealing material layer 6 of this embodiment reduces the difference in thermal expansion between the sealing material layer 6 and the glass substrates 2 and 3 and the transparent conductive films 7 and 8, respectively.
  • the sealing layer 5 based on such a sealing material layer 6 is effective when the thickness is 10 times or more the film thickness of the transparent conductive films 7 and 8. Specifically, it is effective when the thickness of the sealing layer 5 is in the range of 10 to 100 ⁇ m with respect to the transparent conductive films 7 and 8 having a thickness of 0.1 to 1 ⁇ m.
  • the specific thermal expansion coefficient ⁇ 1 of the sealing material layer 6 is preferably in the range of 43 to 72 ( ⁇ 10 ⁇ 7 / ° C.) within the above range, and more preferably 45 to 55 ( ⁇ 10 ⁇ 5). 7 / ° C.). Thermal expansion coefficient alpha 1 of the sealing material layer 6 can be adjusted by the addition amount of the low-expansion filler.
  • the sealing material layer 6 when the sealing material layer 6 is melted by irradiation with laser light, the sealing material layer 6 is locally melted and solidified continuously. For this reason, when the film thickness reduction of the sealing material layer 6 at the time of melting is large, a force is applied to the thin film including the transparent conductive films 7 and 8 formed on the surfaces of the glass substrates 2 and 3 in the peeling direction. It will be. Further, stress based on the reduced film thickness of the sealing material layer 6 is applied to the glass substrates 2 and 3. Since this stress is abruptly applied to the local portion, there is a possibility that the glass substrates 2 and 3 may be cracked or broken.
  • the sealing material layer 6 easily expands while flowing in the line width direction at the time of melting, and the sealing material layer 6 that flows in the line width direction does not return to the original in the subsequent cooling process, and the entire sealing material layer 6 Shrink in the thickness direction. Since the expansion and contraction of the sealing material layer 6 occur locally and continuously, the transparent conductive films 7 and 8 are easily peeled when the sealing material layer 6 contracts. For such a point, it is effective to set the content of the low expansion filler to 20% by volume or more. Thereby, the fluidity of the sealing material layer 6 is moderately suppressed, and peeling of the transparent conductive films 7 and 8 can be suppressed. However, if the content of the low expansion filler is too large, the fluidity of the glass material for sealing is too low, so the content of the low expansion filler is preferably 50% by volume or less.
  • Control of the particle shape of the low expansion filler is also effective in suppressing the decrease in the thickness of the sealing material layer 6.
  • the low expansion filler does not contain particles having a particle diameter exceeding the thickness T of the sealing material layer 6 and is 0.5 T or more and 1 T or less with respect to the film thickness T of the sealing material layer 6. It is preferable to include particles having a particle size in the range of 0.1 to 99% by volume. By using the low expansion filler having such a particle configuration, it is possible to suppress a decrease in the film thickness of the sealing material layer 6.
  • the low expansion filler preferably contains particles having a particle size of 0.5 T or more and 1 T or less in a range of 1 to 50% by volume, and more preferably in a range of 1 to 10% by volume.
  • a low expansion filler containing 0.1% by volume or more and further 1% by volume or more of particles having a particle size of 0.5T or more and 1T or less with respect to the film thickness T of the sealing material layer 6 is used. Thereby, the film thickness reduction at the time of melting and solidifying the sealing material layer 6 can be suppressed.
  • the ratio of particles having a particle size of 0.5T or more and 1T or less exceeds 99% by volume, the content of low expansion filler particles having a particle size of less than 99% is relatively reduced, and sealing is performed. There is a possibility that the distribution of the low expansion filler particles in the adhering material layer 6 becomes non-uniform. In this case, the thermal expansion coefficient of the sealing material layer 6 is partially increased, and cracks or the like are likely to occur in the sealing layer 5 itself.
  • the electronic device 1 of the above-described embodiment is manufactured as follows, for example. First, as shown in FIGS. 3A, 6, and 7, the sealing material layer 6 is formed on the sealing region 3 ⁇ / b> B of the second glass substrate 3. In forming the sealing material layer 6, first, a thermal expansion coefficient ⁇ 1 in a range not less than the larger value of ⁇ 2 value and 0.5 ⁇ 3 value and not more than the smaller value of 2 ⁇ 2 value and ⁇ 3 value. A glass material for sealing having the above is mixed with a vehicle to prepare a sealing material paste.
  • the vehicle is obtained by dissolving a resin as a binder component in a solvent.
  • the resin for the vehicle include cellulose resins such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, nitrocellulose, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, butyl acrylate.
  • Organic resins such as acrylic resins obtained by polymerizing one or more acrylic monomers such as 2-hydroxyethyl acrylate are used.
  • Solvents such as terpineol, butyl carbitol acetate, and ethyl carbitol acetate are used in the case of a cellulose resin, and solvents such as methyl ethyl ketone, terpineol, butyl carbitol acetate, and ethyl carbitol acetate are used in the case of an acrylic resin. .
  • the viscosity of the sealing material paste may be adjusted to the viscosity corresponding to the apparatus applied to the glass substrate 3, and can be adjusted by the ratio of the resin (binder component) and the solvent in the vehicle and the ratio of the sealing glass material and the vehicle.
  • a known additive may be added to the sealing material paste as a glass paste such as an antifoaming agent or a dispersing agent.
  • a known method using a rotary mixer equipped with a stirring blade, a roll mill, a ball mill or the like can be applied to the preparation of the sealing material paste.
  • the above-described sealing material paste is applied to the sealing region 3B of the second glass substrate 3 and dried to form an application layer of the sealing material paste.
  • the sealing material paste is applied to the second sealing region 3B by applying a printing method such as screen printing or gravure printing, or is applied along the second sealing region 3B using a dispenser or the like. To do.
  • the coating layer of the sealing material paste is dried, for example, at a temperature of 120 ° C. or more for 10 minutes or more. A drying process is implemented in order to remove the solvent in an application layer. If the solvent remains in the coating layer, the binder component may be sufficiently decomposed and burned in the subsequent firing step and cannot be removed.
  • the sealing material layer 6 is formed by firing the coating layer of the sealing material paste described above.
  • the coating layer is heated to a temperature not higher than the glass transition point of sealing glass (glass frit), which is the main component of the sealing glass material, and the binder component in the coating layer is removed.
  • the glass material for sealing is heated to a temperature equal to or higher than the softening point of the glass frit to melt and seal the glass material for sealing. In this way, the sealing material layer 6 made of the fired layer of the sealing glass material is formed in the sealing region 3B of the second glass substrate 3.
  • a first glass substrate 2 prepared separately from the second glass substrate 3 is prepared, and using these glass substrates 2 and 3, a solar cell such as a dye-sensitized solar cell, OELD, PDP, An electronic device 1 such as an illumination device using an FPD such as an LCD or an OEL element is manufactured. That is, as shown in FIG. 3B, the first glass substrate 2 and the second glass substrate 3 are laminated via the sealing material layer 6 so that the surfaces 2a and 3a face each other. . A gap is formed between the first glass substrate 2 and the second glass substrate 3 based on the thickness of the sealing material layer 6.
  • the sealing material layer 6 is irradiated with laser light 9 through the second glass substrate 3.
  • the laser beam 9 is irradiated through one of the first and second glass substrates 2 and 3.
  • the laser beam 9 is irradiated while scanning along the frame-shaped sealing material layer 6.
  • a laser beam 9 is irradiated over the entire circumference of the sealing material layer 6 to seal between the first glass substrate 2 and the second glass substrate 3 as shown in FIG.
  • the wearing layer 5 is formed.
  • the glass panel of this embodiment is not restricted to the component of the electronic device 1, It is possible to apply also to glass members (building materials etc.), such as a sealing body of electronic components, or multilayer glass. is there.
  • Laser light 9 is not particularly limited, and laser light from a semiconductor laser, carbon dioxide laser, excimer laser, YAG laser, HeNe laser, or the like is used.
  • the output of the laser beam 9 is appropriately set according to the thickness of the sealing material layer 6 and the like, but is preferably in the range of 2 to 150 W, for example. If the laser output is less than 2 W, the sealing material layer 6 may not be melted, and if it exceeds 150 W, cracks and cracks are likely to occur in the glass substrates 2 and 3.
  • the output of the laser beam is more preferably in the range of 5 to 100W.
  • the transparent conductive film (FTO film) 7 while suppressing defects such as cracks and cracks in the glass substrates 2 and 3 made of soda-lime glass at the time of laser sealing. , 8, and further, peeling of the transparent conductive films (FTO films) 7 and 8 from the glass substrates 2 and 3 can be suppressed. Therefore, it is possible to improve the mechanical reliability, hermetic sealing performance, reliability, and the like of the electronic device 1.
  • the sealing layer 5 of the electronic device 1 is a layer made of a material in which the sealing glass material is melted and fixed. In the electronic device 1 produced as described above, the sealing material layer 6 is melted and cooled. It is a layer formed.
  • the thermal expansion coefficient of the sealing layer 5 is equal to the thermal expansion coefficient alpha 1 of the sealing material layer 6 above.
  • the average particle diameter D50 in this specification means what was measured using the laser diffraction / scattering type particle size distribution measuring apparatus.
  • Example 1 SnO55.7 mol%, SnO 2 3.1 mol%, P 2 O 5 32.5 mol%, ZnO4.8 mol%, Al 2 O 3 2.3 mol%, a composition of SiO 2 1.6 mol% Tin-phosphate glass frit (softening point: 406 ° C.) and zirconium phosphate ((ZrO) 2 P 2 having an average particle size (D50) of 5 ⁇ m and a maximum particle size (Dmax) of 20 ⁇ m as a low expansion filler.
  • a laser absorber having an O 7 ) powder and a composition of Fe 2 O 3 —Cr 2 O 3 —Co 2 O 3 —MnO and a maximum particle size (Dmax) of 7 ⁇ m was prepared.
  • Glass material for sealing by mixing 54 volume% of the tin-phosphate glass frit described above, 43 volume% of zirconium phosphate powder and 3 volume% of the laser absorber (thermal expansion coefficient after firing: 44 ⁇ 10 ⁇ 7 / ° C).
  • a sealing material paste was prepared by mixing 80% by mass of this glass material for sealing with 20% by mass of vehicle.
  • the vehicle was prepared by dissolving 3% by mass of nitrocellulose as a binder component in 97% by mass of a mixed solvent of butyl carbitol acetate (90% by mass) and dibutyl phthalate (10% by mass).
  • a second glass substrate (dimensions: 100 ⁇ 100 ⁇ 1...) Having an FTO film with a thickness of 0.5 ⁇ m on the surface and made of soda lime glass (thermal expansion coefficient: 82 ⁇ 10 ⁇ 7 / ° C.). 1 mmt) was prepared, and a sealing material paste was applied to the sealing region of the glass substrate by a screen printing method (line width: 1 mm), and then dried at 130 ° C. for 5 minutes. By baking the coating layer under the conditions of 450 ° C. ⁇ 10 minutes, a sealing material layer having a film thickness T of 32 ⁇ m was formed.
  • the zirconium phosphate powder as the low expansion filler does not contain particles exceeding the film thickness T, and further contains particles having a particle size of 0.5 T or more and 1 T or less with respect to the film thickness T in the range of 2% by volume. It is out.
  • the sealing material layer is 0.5 times the thermal expansion coefficient ⁇ 2 (38 ⁇ 10 ⁇ 7 / ° C.) of the FTO film and the thermal expansion coefficient ⁇ 3 (82 ⁇ 10 ⁇ 7 / ° C.) of soda lime glass.
  • the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm and an output of 65 W through the second glass substrate at a scanning speed of 5 mm / s to melt and rapidly cool and solidify the sealing material layer.
  • the first glass substrate and the second glass substrate were sealed by forming a sealing layer having a thickness of 30 ⁇ m.
  • the electronic device which sealed the electronic element part with the glass panel was used for the characteristic evaluation mentioned later.
  • Tin-phosphate glass frit having a composition of SnO 59.3 mol%, SnO 2 0.8 mol%, P 2 O 5 33.3 mol%, ZnO 6.0 mol%, SiO 2 0.6 mol% (softening) Point: 367 ° C.), zirconium phosphate ((ZrO) 2 P 2 O 7 ) powder having an average particle size (D50) of 10 ⁇ m and a maximum particle size (Dmax) of 40 ⁇ m as a low expansion filler, Fe 2 O 3 A laser absorber having a composition of —Cr 2 O 3 —Co 2 O 3 —MnO and a maximum particle size (Dmax) of 7 ⁇ m was prepared.
  • Glass material for sealing by mixing 53% by volume of the tin-phosphate glass frit described above, 44% by volume of zirconium phosphate powder and 3% by volume of the laser absorber (thermal expansion coefficient after firing: 46 ⁇ 10 ⁇ 7 / ° C).
  • a sealing material paste was prepared by mixing 80% by mass of this glass material for sealing with 20% by mass of vehicle.
  • the vehicle was prepared by dissolving 3% by mass of nitrocellulose as a binder component in 97% by mass of a mixed solvent of butyl carbitol acetate (90% by mass) and dibutyl phthalate (10% by mass).
  • a second glass substrate (dimensions: 100 ⁇ 100 ⁇ 1...) Having an FTO film with a thickness of 0.5 ⁇ m on the surface and made of soda lime glass (thermal expansion coefficient: 82 ⁇ 10 ⁇ 7 / ° C.). 1 mmt) was prepared, and a sealing material paste was applied to the sealing region of the glass substrate by a screen printing method (line width: 1 mm), and then dried at 130 ° C. for 5 minutes. By baking the coating layer under the conditions of 450 ° C. ⁇ 10 minutes, a sealing material layer having a film thickness T of 62 ⁇ m was formed.
  • the zirconium phosphate powder as the low expansion filler does not contain particles exceeding the film thickness T, and further contains particles having a particle diameter of 0.5 T or more and 1 T or less with respect to the film thickness T in the range of 1% by volume. It is out.
  • the sealing material layer is 0.5 times the thermal expansion coefficient ⁇ 2 (38 ⁇ 10 ⁇ 7 / ° C.) of the FTO film and the thermal expansion coefficient ⁇ 3 (82 ⁇ 10 ⁇ 7 / ° C.) of soda lime glass.
  • the sealing material layer is irradiated with laser light (semiconductor laser) having a wavelength of 940 nm and an output of 85 W through the second glass substrate at a scanning speed of 10 mm / s to melt and rapidly solidify the sealing material layer.
  • laser light semiconductor laser
  • the first glass substrate and the second glass substrate were sealed.
  • the electronic device in which the electronic element portion was sealed with the glass panel was subjected to the characteristic evaluation described later.
  • Tin-phosphate glass frit having a composition of SnO 63.3 mol%, SnO 2 2.5 mol%, P 2 O 5 28.8 mol%, ZnO 4.9 mol%, Al 2 O 3 0.5 mol% (Softening point: 366 ° C.), zirconium phosphate ((ZrO) 2 P 2 O 7 ) powder having an average particle size (D50) of 12 ⁇ m and a maximum particle size (Dmax) of 45 ⁇ m as a low expansion filler, Fe 2 A laser absorber having an O 3 —Cr 2 O 3 —Co 2 O 3 —MnO composition and a maximum particle size (Dmax) of 10 ⁇ m was prepared.
  • Glass material for sealing by mixing 63 volume% of the tin-phosphate glass frit described above, 34 volume% of zirconium phosphate powder, and 3 volume% of the laser absorber (thermal expansion coefficient after firing: 52 ⁇ 10 ⁇ 7 / ° C).
  • a sealing material paste was prepared by mixing 80% by mass of this glass material for sealing with 20% by mass of vehicle.
  • the vehicle was prepared by dissolving 3% by mass of nitrocellulose as a binder component in 97% by mass of a mixed solvent of butyl carbitol acetate (90% by mass) and dibutyl phthalate (10% by mass).
  • a second glass substrate (dimensions: 100 ⁇ 100 ⁇ 1...) Having an FTO film with a thickness of 0.5 ⁇ m on the surface and made of soda lime glass (thermal expansion coefficient: 82 ⁇ 10 ⁇ 7 / ° C.). 1 mmt) was prepared, and a sealing material paste was applied to the sealing region of the glass substrate by a screen printing method (line width: 1 mm), and then dried at 130 ° C. for 5 minutes. By baking the coating layer under the conditions of 450 ° C. ⁇ 10 minutes, a sealing material layer having a film thickness T of 65 ⁇ m was formed.
  • the zirconium phosphate powder as the low expansion filler does not contain particles exceeding the film thickness T, and further contains particles having a particle diameter of 0.5 T or more and 1 T or less with respect to the film thickness T in the range of 5% by volume. It is out.
  • the sealing material layer is 0.5 times the thermal expansion coefficient ⁇ 2 (38 ⁇ 10 ⁇ 7 / ° C.) of the FTO film and the thermal expansion coefficient ⁇ 3 (82 ⁇ 10 ⁇ 7 / ° C.) of soda lime glass.
  • the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 940 nm and an output of 72 W through the second glass substrate at a scanning speed of 5 mm / s to melt and rapidly solidify the sealing material layer.
  • a laser beam semiconductor laser
  • Example 4 In Example 3 described above, a sealing glass material prepared by mixing 75% by volume of tin-phosphate glass frit, 22% by volume of zirconium phosphate powder and 3% by volume of a laser absorber (thermal expansion coefficient after firing) : 72 ⁇ 10 ⁇ 7 / ° C.), a sealing material layer was formed in the same manner as in Example 3, and the first glass substrate and the second glass substrate were sealed. Thus, the electronic device in which the electronic element portion was sealed with the glass panel was subjected to the characteristic evaluation described later.
  • the sealing material layer is 0.5 times the thermal expansion coefficient ⁇ 2 (38 ⁇ 10 ⁇ 7 / ° C.) of the FTO film and the thermal expansion coefficient ⁇ 3 (82 ⁇ 10 ⁇ 7 / ° C.) of soda lime glass.
  • Example 3 (Comparative Example 1)
  • a sealing glass material prepared by mixing 52% by volume of a tin-phosphate glass frit, 45% by volume of zirconium phosphate powder, and 3% by volume of a laser absorber (thermal expansion coefficient after firing) : 37 ⁇ 10 ⁇ 7 / ° C.), a sealing material layer was formed in the same manner as in Example 3, and the first glass substrate and the second glass substrate were sealed.
  • the electronic device in which the electronic element portion was sealed with the glass panel was subjected to the characteristic evaluation described later.
  • the thermal expansion coefficient ⁇ 1 (37 ⁇ 10 ⁇ 7 / ° C.) of the sealing material layer is twice as large as the thermal expansion coefficient ⁇ 2 (38 ⁇ 10 ⁇ 7 / ° C.) of the FTO film (76 ⁇ 10 ⁇ 7 / ° C.).
  • Example 2 (Comparative Example 2) In Example 3 described above, a sealing glass material prepared by mixing 83% by volume of a tin-phosphate glass frit, 14% by volume of zirconium phosphate powder, and 3% by volume of a laser absorber (thermal expansion coefficient after firing) : 81 ⁇ 10 ⁇ 7 / ° C.), a sealing material layer was formed in the same manner as in Example 3, and the first glass substrate and the second glass substrate were sealed. Thus, the electronic device in which the electronic element portion was sealed with the glass panel was subjected to the characteristic evaluation described later.
  • the thermal expansion coefficient ⁇ 1 (81 ⁇ 10 ⁇ 7 / ° C.) of the sealing material layer is equal to the thermal expansion coefficient ⁇ 2 (38 ⁇ 10 ⁇ 7 / ° C.) of the FTO film and the thermal expansion coefficient ⁇ of soda lime glass.
  • the thermal expansion of the FTO film Either a value twice the coefficient ⁇ 2 (38 ⁇ 10 ⁇ 7 / ° C.) (76 ⁇ 10 ⁇ 7 / ° C.) or a value of the thermal expansion coefficient ⁇ 3 (82 ⁇ 10 ⁇ 7 / ° C.) of soda lime glass It is a value larger than a small value (76 ⁇ 10 ⁇ 7 / ° C.).
  • a glass material for sealing (thermal expansion coefficient after firing: 46 ⁇ 10 ⁇ 7 / ° C.) is prepared by mixing 55% by volume of the bismuth-based glass frit, 43% by volume of cordierite powder, and 2% by volume of the laser absorber. did.
  • a sealing material paste was prepared by mixing 80% by mass of this glass material for sealing with 20% by mass of vehicle.
  • the vehicle was prepared by dissolving 5% by mass of ethyl cellulose as a binder component in 95% by mass of a mixed solvent of butyl carbitol acetate (89% by mass) and terpineol (11% by mass).
  • a second glass substrate (dimension: 100 ⁇ 100 ⁇ 1...) Having an FTO film having a thickness of 0.5 ⁇ m on the surface and made of soda lime glass (thermal expansion coefficient: 86 ⁇ 10 ⁇ 7 / ° C.). 1 mmt) was prepared, and a sealing material paste was applied to the sealing region of the glass substrate by a screen printing method (line width: 1 mm), and then dried at 130 ° C. for 5 minutes. By baking the coating layer under the conditions of 450 ° C. ⁇ 10 minutes, a sealing material layer having a film thickness T of 65 ⁇ m was formed.
  • the cordierite powder as the low expansion filler does not contain particles exceeding the film thickness T, and further contains particles having a particle diameter of 0.5 T or more and 1 T or less with respect to the film thickness T in the range of 3% by volume. Yes.
  • the sealing material layer is 0.5 times the thermal expansion coefficient ⁇ 2 (38 ⁇ 10 ⁇ 7 / ° C.) of the FTO film and the thermal expansion coefficient ⁇ 3 (86 ⁇ 10 ⁇ 7 / ° C.) of soda lime glass.
  • the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 808 nm and an output of 85 W through the second glass substrate at a scanning speed of 10 mm / s to melt and rapidly solidify the sealing material layer.
  • a laser beam semiconductor laser
  • Example 6 Bismuth glass frit having a composition of 83.1% by weight of Bi 2 O 3, 5.6% by weight of B 2 O 3 , 10.8% by weight of ZnO and 0.5% by weight of Al 2 O 3 (softening point: 418 ° C.) 74% by volume, 24% by volume of cordierite powder, and 2% by volume of the laser absorber were mixed to prepare a glass material for sealing (thermal expansion coefficient after firing: 70 ⁇ 10 ⁇ 7 / ° C.). A sealing material paste was prepared by mixing 80% by mass of this glass material for sealing with 20% by mass of vehicle.
  • the vehicle was prepared by dissolving 5% by mass of ethyl cellulose as a binder component in 95% by mass of a mixed solvent of butyl carbitol acetate (89% by mass) and terpineol (11% by mass).
  • a second glass substrate (dimension: 100 ⁇ 100 ⁇ 1...) Having an FTO film having a thickness of 0.5 ⁇ m on the surface and made of soda lime glass (thermal expansion coefficient: 86 ⁇ 10 ⁇ 7 / ° C.). 1 mmt) was prepared, and a sealing material paste was applied to the sealing region of the glass substrate by a screen printing method (line width: 1 mm), and then dried at 130 ° C. for 5 minutes. By baking the coating layer under the conditions of 450 ° C. ⁇ 10 minutes, a sealing material layer having a film thickness T of 65 ⁇ m was formed.
  • the cordierite powder as the low expansion filler does not contain particles exceeding the film thickness T, and further contains particles having a particle diameter of 0.5 T or more and 1 T or less with respect to the film thickness T in the range of 3% by volume. Yes.
  • the sealing material layer is 0.5 times the thermal expansion coefficient ⁇ 2 (38 ⁇ 10 ⁇ 7 / ° C.) of the FTO film and the thermal expansion coefficient ⁇ 3 (86 ⁇ 10 ⁇ 7 / ° C.) of soda lime glass.
  • the sealing material layer is irradiated with a laser beam (semiconductor laser) having a wavelength of 808 nm and an output of 85 W through the second glass substrate at a scanning speed of 10 mm / s to melt and rapidly solidify the sealing material layer.
  • a laser beam semiconductor laser
  • Example 3 (Comparative Example 3)
  • a sealing glass material prepared by mixing 47% by volume of bismuth-based glass frit, 51% by volume of cordierite powder, and 2% by volume of a laser absorber (coefficient of thermal expansion after firing: 34 ⁇ 10
  • a sealing material layer was formed in the same manner as in Example 5 except that ⁇ 7 / ° C. was used, and the first glass substrate and the second glass substrate were sealed.
  • the electronic device in which the electronic element portion was sealed with the glass panel was subjected to the characteristic evaluation described later.
  • the thermal expansion coefficient ⁇ 1 (34 ⁇ 10 ⁇ 7 / ° C.) of the sealing material layer is twice as large as the thermal expansion coefficient ⁇ 2 (38 ⁇ 10 ⁇ 7 / ° C.) of the FTO film (76 ⁇ 10 ⁇ 7 / ° C.).
  • the thermal expansion of the FTO film Either a coefficient ⁇ 2 (38 ⁇ 10 ⁇ 7 / ° C.) or a value (43 ⁇ 10 ⁇ 7 / ° C.) that is 0.5 times the thermal expansion coefficient ⁇ 3 (86 ⁇ 10 ⁇ 7 / ° C.) of soda lime glass It is a smaller value than a large value (43 ⁇ 10 ⁇ 7 / ° C.).
  • Comparative Example 4 Glass material for sealing produced by mixing 81% by volume of a bismuth-based glass frit having the same composition as in Example 5, 17% by volume of cordierite powder, and 2% by volume of a laser absorber (thermal expansion coefficient after firing: 82 ⁇ 10 A sealing material layer was formed in the same manner as in Example 6 except that ⁇ 7 / ° C. was used, and the first glass substrate and the second glass substrate were sealed. Thus, the electronic device in which the electronic element portion was sealed with the glass panel was subjected to the characteristic evaluation described later.
  • the thermal expansion coefficient ⁇ 1 (82 ⁇ 10 ⁇ 7 / ° C.) of the sealing material layer is equal to the thermal expansion coefficient ⁇ 2 (38 ⁇ 10 ⁇ 7 / ° C.) of the FTO film and the thermal expansion coefficient ⁇ of soda lime glass.
  • the thermal expansion of the FTO film is 0.5 times the value (43 ⁇ 10 ⁇ 7 / ° C.), which is greater than the value (43 ⁇ 10 ⁇ 7 / ° C.), which is larger than 3 (86 ⁇ 10 ⁇ 7 / ° C.).
  • Example 5 Glass material for sealing produced by mixing 93% by volume of bismuth glass frit having the same composition as in Example 5, 5% by volume of cordierite powder, and 2% by volume of laser absorber (coefficient of thermal expansion after firing: 101 ⁇ 10 A sealing material layer was formed in the same manner as in Example 6 except that ⁇ 7 / ° C. was used, and the first glass substrate and the second glass substrate were sealed. Thus, the electronic device in which the electronic element portion was sealed with the glass panel was subjected to the characteristic evaluation described later.
  • the thermal expansion coefficient ⁇ 1 (101 ⁇ 10 ⁇ 7 / ° C.) of the sealing material layer is equal to the thermal expansion coefficient ⁇ 2 (38 ⁇ 10 ⁇ 7 / ° C.) of the FTO film and the thermal expansion coefficient ⁇ of soda lime glass.
  • thermo expansion coefficient (alpha) 1 described in the column of the glass material for sealing shows the thermal expansion coefficient of the glass material for sealing after baking (namely, material of the sealing material layer).
  • the glass panels according to Examples 1 to 5 are excellent in appearance and airtightness, with no cracks or peeling in the FTO film.
  • Comparative Example 1 cracks occurred in the FTO film, and in Comparative Example 2, cracks and peeling occurred in the FTO film, and none of them could obtain airtightness.
  • Comparative Example 3 the sealing material layer could not be bonded to the glass substrate.
  • Comparative Example 4 the FTO film cracks and the first glass substrate cracks.
  • the FTO film cracks and peels, and the first glass substrate cracks, both of which are airtight. could not get.
  • the glass member with a sealing material layer of the present invention manufactures a solar cell panel or a flat display device having a structure in which a solar cell element or a display element is sealed between two glass substrates arranged to face each other. Therefore, it is useful as a glass substrate used for this purpose.
  • the electronic device of the present invention is a solar cell panel or a flat display device having the above structure.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Optics & Photonics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electromagnetism (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Glass Compositions (AREA)
  • Photovoltaic Devices (AREA)
  • Electroluminescent Light Sources (AREA)
  • Hybrid Cells (AREA)

Abstract

Pour empêcher un film conducteur transparent de se fissurer ou de s'enlever par pelage du substrat de verre constitué d'un verre sodocalcique tout en empêchant le substrat de verre de subir une fissuration, une rupture, etc. pendant le scellage au laser, un substrat de verre (3) constitué de verre sodocalcique possède une surface (3a) comprenant une région de scellement étanche et possède un film conducteur transparent (film de FTO) (8) formé sur la surface (3a). La région de scellement étanche possède, disposée sur celle-ci, une couche (6) de matériau d'étanchéité constituée d'une couche brûlée d'un matériau de verre pour un scellement étanche qui comprend un verre de scellement étanche, une charge à faible expansion et une matière absorbant la lumière laser. La couche (6) de matériau d'étanchéité a un coefficient de dilatation thermique α1, qui est égal ou supérieur au plus grand du coefficient de dilatation thermique α2 du film conducteur transparent (8) et une moitié du coefficient de dilatation thermique α3 du substrat de verre (3) et qui est égal ou inférieur au plus petit de 2 fois le coefficient de dilatation thermique α2 et du coefficient de dilatation thermique α3.
PCT/JP2010/059043 2009-05-28 2010-05-27 Élément de verre avec une couche de matériau d'étanchéité attachée à celui-ci, dispositif électronique obtenu à l'aide de celui-ci et son procédé de fabrication WO2010137667A1 (fr)

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JP2009128679 2009-05-28

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013049614A (ja) * 2011-07-29 2013-03-14 Nippon Electric Glass Co Ltd 封着材料層付きガラス基板の製造方法
US8697242B2 (en) 2009-06-30 2014-04-15 Asahi Glass Company, Limited Glass member provided with sealing material layer, electronic device using it and process for producing the electronic device
US9938183B2 (en) * 2014-10-28 2018-04-10 Boe Technology Group Co., Ltd. Sealing glass paste
JP2019179794A (ja) * 2018-03-30 2019-10-17 Tdk株式会社 薄膜キャパシタ

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI483408B (zh) * 2012-08-30 2015-05-01 Giga Solar Materials Corp 摻有玻璃粉末之染料敏化太陽能電池及其製作方法
CN112125511B (zh) * 2020-09-28 2022-04-12 成都光明光电股份有限公司 光学玻璃

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008059802A (ja) * 2006-08-29 2008-03-13 Univ Of Tokyo パネル体の製造方法
JP2008115057A (ja) * 2006-11-07 2008-05-22 Electric Power Dev Co Ltd 封止材料、ガラスパネルの製造方法および色素増感太陽電池
JP2009037861A (ja) * 2007-08-01 2009-02-19 Sharp Corp 色素増感型太陽電池モジュール

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008059802A (ja) * 2006-08-29 2008-03-13 Univ Of Tokyo パネル体の製造方法
JP2008115057A (ja) * 2006-11-07 2008-05-22 Electric Power Dev Co Ltd 封止材料、ガラスパネルの製造方法および色素増感太陽電池
JP2009037861A (ja) * 2007-08-01 2009-02-19 Sharp Corp 色素増感型太陽電池モジュール

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8697242B2 (en) 2009-06-30 2014-04-15 Asahi Glass Company, Limited Glass member provided with sealing material layer, electronic device using it and process for producing the electronic device
JP2013049614A (ja) * 2011-07-29 2013-03-14 Nippon Electric Glass Co Ltd 封着材料層付きガラス基板の製造方法
US9938183B2 (en) * 2014-10-28 2018-04-10 Boe Technology Group Co., Ltd. Sealing glass paste
JP2019179794A (ja) * 2018-03-30 2019-10-17 Tdk株式会社 薄膜キャパシタ

Also Published As

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JPWO2010137667A1 (ja) 2012-11-15

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