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WO2019167549A1 - Poudre de verre et matériau d'étanchéité l'utilisant - Google Patents

Poudre de verre et matériau d'étanchéité l'utilisant Download PDF

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Publication number
WO2019167549A1
WO2019167549A1 PCT/JP2019/003769 JP2019003769W WO2019167549A1 WO 2019167549 A1 WO2019167549 A1 WO 2019167549A1 JP 2019003769 W JP2019003769 W JP 2019003769W WO 2019167549 A1 WO2019167549 A1 WO 2019167549A1
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WIPO (PCT)
Prior art keywords
sealing material
glass
material layer
laser
sealing
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2019/003769
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English (en)
Japanese (ja)
Inventor
将行 廣瀬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Publication date
Priority claimed from JP2018073042A external-priority patent/JP2019151539A/ja
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Publication of WO2019167549A1 publication Critical patent/WO2019167549A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • C03C8/24—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
    • H10W76/60—

Definitions

  • the present invention relates to a glass powder and a sealing material using the glass powder, and more particularly to a glass powder suitable for a sealing process using a laser beam (hereinafter referred to as laser sealing) and a sealing material using the glass powder.
  • laser sealing a glass powder suitable for a sealing process using a laser beam (hereinafter referred to as laser sealing) and a sealing material using the glass powder.
  • the sealing material containing glass powder is less permeable to gas and moisture than the organic resin adhesive, the characteristics of the internal element can be maintained over a long period of time.
  • the glass powder has a higher softening temperature than the organic resin adhesive, there is a risk that the internal element is thermally deteriorated during sealing. Under such circumstances, laser sealing has attracted attention. According to laser sealing, only the portion to be sealed can be locally heated, so that the hermetic package can be sealed without thermally deteriorating the internal elements.
  • Bismuth glass is generally used as a glass powder for laser sealing.
  • Bismuth-based glass has a feature that its water resistance is higher than other low-melting-point glasses.
  • the present invention has been made in view of the above circumstances, and its technical problem is that it has high water resistance and can be softened and flowed at a low temperature during laser sealing, and a sealing material using the same. Is to invent.
  • the present inventor has found that the above technical problem can be solved by introducing a predetermined amount of a specific transition metal oxide into silver phosphate glass, and proposes the present invention.
  • the glass powder of the present invention has a glass composition of mol% in terms of the following oxides: Ag 2 O 10 to 50%, P 2 O 5 10 to less than 35%, TeO 2 1 to less than 35%, ZnO 3 More than 25%, Nb 2 O 5 0-10%, CuO + MnO + Fe 2 O 3 + V 2 O 5 + NiO + WO 3 + MoO 3 + Co 3 O 4 1-30%.
  • CuO + MnO + Fe 2 O 3 + V 2 O 5 + NiO + WO 3 + MoO 3 + Co 3 O 4 means CuO, MnO, Fe 2 O 3 , V 2 O 5 , NiO, WO 3 , MoO 3 and Co 3 O 4 . Refers to total amount.
  • the glass powder of the present invention contains Ag 2 O 10 to 50%, P 2 O 5 10 to less than 35%, TeO 2 1 to less than 35%, ZnO 3 to less than 25%, and Nb 2 O 5 0 to 10%. contains. If it does in this way, glass can be made low melting
  • the glass powder of the present invention comprises CuO + MnO + Fe 2 O 3 + V 2 O 5 + NiO + WO 3 + MoO 3 + Co 3 O 4 to 1 mol% or more. In this way, the light absorption characteristics are improved, so that the glass is softened and fluidized easily during laser sealing.
  • the glass powder of the present invention preferably has a CuO + MnO content of 1 to 30 mol%.
  • CuO + MnO is the total amount of CuO and MnO.
  • the glass powder of the present invention does not substantially contain PbO.
  • substantially does not contain PbO refers to a case where the content of PbO in the glass composition is less than 0.1 mol%.
  • the sealing material of the present invention contains glass powder 50 to 90% by volume, refractory filler powder 10 to 50% by volume, laser absorber 0 to 20% by volume, and the glass powder is preferably the above glass powder. .
  • the refractory filler powder is NaZr 2 (PO 4 ) type 3 solid solution, willemite, cordierite, zircon, tin oxide, ⁇ -eucryptite, zirconium phosphate, niobium pentoxide, quartz. It is preferably one or more selected from glass, mullite, aluminum titanate, alumina, cubic zirconia, titania, zinc stannate, magnesia, quartz, spinel and garnite.
  • the “NaZr 2 (PO 4 ) 3 type solid solution” is a substance represented by the chemical formula of XY 2 Z 3 O 12 or AYZ 3 O 12 , where X is a monovalent element, Is composed of an element corresponding to tetravalent, and A and Z are composed of an element corresponding to pentavalent.
  • the content of the laser absorber is preferably 5% by volume or less. If it does in this way, it will become difficult to devitrify glass at the time of laser sealing.
  • the sealing material of the present invention is preferably used for laser sealing. In this way, it is possible to prevent thermal degradation of the internal elements during sealing.
  • the light source of the laser beam used for laser sealing is not particularly limited, but for example, a semiconductor laser, a YAG laser, a CO 2 laser, an excimer laser, an infrared laser, and the like are preferable in terms of easy handling.
  • the emission center wavelength of the laser beam is preferably 500 to 1600 nm, particularly preferably 750 to 1300 nm, in order for the sealing material to absorb the laser beam accurately.
  • the hermetic package of the present invention is an airtight package in which a package base and a glass lid are hermetically sealed via a sealing material layer, and the sealing material layer preferably contains the sealing material described above.
  • the package base has a base portion and a frame portion provided on the base portion, and a sealing material layer is interposed between the top portion of the frame portion and the glass lid. preferable.
  • the glass powder of the present invention has a glass composition of mol% in terms of the following oxides: Ag 2 O 10 to 50%, P 2 O 5 10 to less than 35%, TeO 2 1 to 35%, ZnO 3 more than Less than 25%, Nb 2 O 5 0-10%, CuO + MnO + Fe 2 O 3 + V 2 O 5 + NiO + WO 3 + MoO 3 + Co 3 O 4 1-30%.
  • the reason for limiting the glass composition of the glass powder as described above will be described in detail below.
  • the following% display shows mol% unless there is particular notice.
  • Ag 2 O is a component that increases the water resistance because it lowers the melting point of the glass and hardly dissolves in water.
  • the content of Ag 2 O is 10 to 50%, preferably 20 to 40%.
  • Ag 2 O is too small, the viscosity of the glass becomes high, the softening fluidity tends to decrease, the water resistance tends to decrease.
  • vitrification tends to be difficult.
  • P 2 O 5 is a component that lowers the melting point of glass. Its content is 10 to less than 35%, preferably 15 to 25%. When the P 2 O 5 is too small, vitrification tends to be difficult. On the other hand, if the P 2 O 5 is too large, weather resistance, water resistance tends to decrease.
  • TeO 2 is a component that enhances devitrification resistance and is a component that lowers the melting point of glass.
  • the content of TeO 2 is 1 to less than 35%, preferably 10 to 25%.
  • TeO 2 is too small, it becomes difficult to enjoy the above-mentioned effects.
  • TeO 2 is too large, weather resistance, water resistance tends to decrease.
  • ZnO is a component that increases devitrification resistance and a component that decreases the thermal expansion coefficient.
  • the ZnO content is more than 3 to less than 25%, preferably 5 to 20%.
  • ZnO When there is too little ZnO, it will become difficult to enjoy the said effect.
  • ZnO when there is too much ZnO, the viscosity of glass will become high and softening fluidity
  • Nb 2 O 5 is a component that improves water resistance.
  • the content of Nb 2 O 5 is 0 to 10%, preferably 1 to 8%. If nb 2 O 5 is too large, the viscosity of the glass becomes high, the softening fluidity tends to decrease.
  • CuO, MnO, Fe 2 O 3 , V 2 O 5 , NiO, WO 3 , MoO 3 , and Co 3 O 4 are components that enhance light absorption characteristics.
  • the content of CuO + MnO + Fe 2 O 3 + V 2 O 5 + NiO + WO 3 + MoO 3 + Co 3 O 4 is 1-30%, preferably 2-25%, especially 3-20%. If the amount of CuO + MnO + Fe 2 O 3 + V 2 O 5 + NiO + WO 3 + MoO 3 + Co 3 O 4 is too small, the glass becomes difficult to soften and flow during laser sealing, so the laser sealing strength tends to decrease. On the other hand, if there is too much CuO + MnO + Fe 2 O 3 + V 2 O 5 + NiO + WO 3 + MoO 3 + Co 3 O 4 , vitrification becomes difficult.
  • CuO and MnO have good light absorption characteristics and are compatible with silver phosphate glass. Good properties.
  • the content of CuO + MnO is 1 to 30%, preferably 2 to 25%, especially 3 to 20%. If the amount of CuO + MnO is too small, the glass is softened and hardly flows during laser sealing, so that the laser sealing strength tends to decrease. On the other hand, if there is too much CuO + MnO, vitrification becomes difficult.
  • the contents of CuO, MnO, Fe 2 O 3 , V 2 O 5 , NiO, WO 3 , MoO 3 and Co 3 O 4 are preferably 0 to 25%, more preferably 2 to 20%, Particularly preferred is 3 to 10%.
  • oxides such as Li 2 O, SiO 2 , Al 2 O 3 , In 2 O 3 , Bi 2 O 3 , Li, Si, B Al, Mn, In, Mo, Cu, Co, Ge, W, Zn, Te, Ga, P, and Ag halides and sulfides can be introduced up to 5%, preferably 1%, respectively.
  • halide refers to fluoride, chloride, bromide, and iodide. When the metal elements are the same, the halide is more effective in reducing the viscosity of the glass than the oxide, but the environmental load is increased.
  • the glass powder of the present invention has a thermal expansion coefficient of about 100 to 200 ⁇ 10 ⁇ 7 / ° C. in a temperature range of 30 to 150 ° C., and does not have high mechanical strength. Therefore, the glass powder of the present invention is preferably mixed with the refractory filler powder to form a composite powder. Thereby, mechanical strength can be raised, reducing a thermal expansion coefficient.
  • the sealing material of the present invention preferably contains glass powder 50 to 90 volume%, refractory filler powder 10 to 50 volume%, laser absorber 0 to 20 volume%, glass powder 55 to 80 volume%, fire resistance More preferably, it contains 20 to 45% by volume of a filler powder and 0 to 5% by volume of a laser absorber.
  • the glass powder is a component that softens and flows during laser sealing to ensure the hermetic reliability of the hermetic package.
  • the refractory filler powder is a component that acts as an aggregate and increases the mechanical strength while reducing the thermal expansion coefficient.
  • the laser absorbing material is a component that absorbs laser light and promotes the softening flow of the glass powder during laser sealing.
  • the maximum particle diameter Dmax of the glass powder is preferably 10 ⁇ m or less, particularly 5 ⁇ m or less.
  • the “maximum particle diameter D max ” refers to a value measured by a laser diffractometer, and in the volume-based cumulative particle size distribution curve measured by the laser diffraction method, the accumulated amount is accumulated from the smaller particle.
  • the particle size is 99%.
  • the softening point of the glass powder is preferably 400 ° C. or lower, 380 ° C. or lower, particularly 360 ° C. or lower. If the softening point of the glass powder is too high, the glass is difficult to soften during laser sealing, so the laser sealing strength cannot be increased unless the output of the laser beam is increased.
  • the “softening point” refers to the temperature at the fourth inflection point when measured by macro-type differential thermal analysis.
  • refractory filler powder Various materials can be used for the refractory filler powder. Among them, from the viewpoint of low expansion and high strength, NaZr 2 (PO 4 ) type 3 solid solution, willemite, cordierite, zircon, tin oxide, ⁇ - Eucryptite, zirconium phosphate, niobium pentoxide, quartz glass, mullite, aluminum titanate and the like are preferable. From the viewpoint of increasing the mechanical strength, it is also preferable to use alumina, cubic zirconia, titania, zinc stannate, magnesia, quartz, spinel, garnite or the like as the refractory filler powder.
  • said refractory filler powder may be used independently, and 2 or more types may be mixed and used for it.
  • the maximum particle diameter D max of the refractory filler powder is preferably 15 ⁇ m or less, less than 10 ⁇ m, less than 5 ⁇ m, particularly less than 0.5 to 3 ⁇ m. If the maximum particle diameter Dmax of the refractory filler powder is too large, it is difficult to make the gap between the objects to be sealed uniform, it is difficult to narrow the gap between the objects to be sealed, and it is difficult to reduce the thickness of the hermetic package. Note that when the gap between the objects to be sealed is large and the difference in thermal expansion coefficient between the objects to be sealed and the sealing material layer is large, cracks or the like are likely to occur in the objects to be sealed or the sealing material layer.
  • the content of the laser absorber is preferably 0 to 20% by volume, 0 to 10% by volume, 0 to 5% by volume, 0 to 3% by volume, 0 to 1% by volume, particularly 0. ⁇ 0.1% by volume.
  • a laser absorber will melt in glass at the time of laser sealing, and this will devitrify glass, and it will become easy to fall the softening fluidity of a sealing material.
  • the light absorptance in monochromatic light having a wavelength of 808 nm is preferably 20% or more, more preferably 30% or more. If this light absorptance is low, the sealing material layer cannot absorb light properly at the time of laser sealing, and the laser sealing strength cannot be increased unless the output of the laser light is increased. If the output of the laser beam is increased, the internal element may be thermally deteriorated during laser sealing.
  • the thermal expansion coefficient is preferably 85 ⁇ 10 ⁇ 7 / ° C. or less, 80 ⁇ 10 ⁇ 7 / ° C. or less, particularly 50 ⁇ 10 ⁇ 7 / ° C. or more, and 75 ⁇ 10 ⁇ 7 / ° C. It is below °C. In this way, when the sealed object has a low expansion, thermal distortion is hardly generated in the sealed object or the sealing material during laser sealing, and a crack occurs in the sealed object or the sealing material layer. It becomes difficult.
  • the softening point is preferably 500 ° C. or lower, 450 ° C. or lower, particularly 400 ° C. or lower. If the softening point of the sealing material is too high, the glass becomes difficult to soften and flow during laser sealing, so the laser sealing strength cannot be increased unless the output of the laser beam is increased.
  • the sealing material of the present invention is prepared by first preparing various raw materials so as to have the above glass composition, melting at 850 to 1000 ° C. for 1 to 3 hours to vitrify, forming the molten glass into a film, and further ball milling, Air classification is performed to obtain glass powder. Then, a sealing material can be obtained by adding and mixing a refractory filler powder etc. to this glass powder.
  • the sealing material of the present invention may be used in the form of powder, but it is easy to handle if it is uniformly kneaded with a vehicle and processed into a sealing material paste.
  • the vehicle is mainly composed of a solvent and a resin.
  • the resin is added for the purpose of adjusting the viscosity of the sealing material paste.
  • surfactant, a thickener, etc. can also be added as needed.
  • the sealing material paste is applied to an object to be sealed using an applicator such as a dispenser or a screen printer, and then subjected to a binder removal step.
  • acrylic acid ester (acrylic resin), ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, methacrylic acid ester and the like can be used.
  • acrylic acid esters and nitrocellulose are preferable because they have good thermal decomposability.
  • Solvents include N, N'-dimethylformamide (DMF), ⁇ -terpineol, higher alcohol, ⁇ -butyllactone ( ⁇ -BL), tetralin, butyl carbitol acetate, ethyl acetate, isoamyl acetate, diethylene glycol monoethyl ether, diethylene glycol Monoethyl ether acetate, benzyl alcohol, toluene, 3-methoxy-3-methylbutanol, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene Glycol monobutyl ether, propylene carbonate, dimethyl sulfoxide (DMSO), N-methyl -2-pyrrolidone and the like can be used.
  • DMF dimethylformamide
  • ⁇ -BL ⁇ -butyllactone
  • the sealing material of the present invention is preferably used for a sealing material layer of an airtight package.
  • the hermetic package preferably has a structure in which the package base and the glass lid are hermetically sealed via a sealing material layer.
  • the airtight package will be described in detail.
  • the package base preferably has a base and a frame provided on the base, and the sealing material layer is preferably formed on the top of the frame. If it does in this way, it will become easy to accommodate internal elements, such as MEMS and a LED element, in the frame part of a package base.
  • the frame portion of the package base is preferably formed in a frame shape along the outer edge region of the package base. In this way, the effective area that functions as a device can be expanded. In addition, it becomes easy to accommodate internal elements such as MEMS and LED elements in the frame portion of the package base, and it is also easy to perform wiring bonding and the like.
  • the surface roughness Ra of the surface of the region where the sealing material layer is disposed at the top of the frame is preferably less than 1.0 ⁇ m. If the surface roughness Ra of the surface increases, the accuracy of laser sealing tends to decrease.
  • the “surface roughness Ra” can be measured by, for example, a stylus type or non-contact type laser film thickness meter or surface roughness meter.
  • the width of the top of the frame is preferably 100 to 3000 ⁇ m, 200 to 1500 ⁇ m, particularly 300 to 900 ⁇ m. If the width of the top of the frame is too narrow, it is difficult to align the sealing material layer and the top of the frame. On the other hand, if the width of the top of the frame is too wide, the effective area that functions as a device is reduced.
  • the package substrate is preferably made of glass, glass ceramic, aluminum nitride, or aluminum oxide, or a composite material thereof (for example, aluminum nitride and glass ceramic integrated). Since glass easily forms a sealing material layer and a reaction layer, a strong sealing strength can be secured by laser sealing.
  • the glass ceramic has a feature that it is easy to optimize the wettability with the sealing material layer. Furthermore, since the thermal via can be easily formed, it is possible to appropriately prevent the temperature of the hermetic package from rising excessively. Since aluminum nitride and aluminum oxide have good heat dissipation, it is easy to suppress the temperature rise of the hermetic package.
  • the glass ceramic, aluminum nitride, and aluminum oxide preferably have a black pigment dispersed (sintered in a state in which the black pigment is dispersed).
  • the package base can absorb the laser light transmitted through the sealing material layer.
  • the portion of the package base that comes into contact with the sealing material layer is heated during laser sealing, so that the formation of the reaction layer can be promoted at the interface between the sealing material layer and the package base.
  • the package substrate in which the black pigment is dispersed has the property of absorbing the laser beam to be irradiated, that is, the thickness is 0.5 mm, and the total light transmittance at the wavelength of the laser beam to be irradiated (808 nm) is 10% or less ( Desirably, it is preferably 5% or less. If it does in this way, it will become easy to raise the temperature of a sealing material layer in the interface of a package base
  • the thickness of the base of the package substrate is preferably 0.1 to 2.5 mm, particularly preferably 0.2 to 1.5 mm. Thereby, thickness reduction of an airtight package can be achieved.
  • the height of the frame portion of the package substrate that is, the height obtained by subtracting the thickness of the base portion from the package substrate is preferably 100 to 2000 ⁇ m, particularly 200 to 900 ⁇ m. In this way, it becomes easy to reduce the thickness of the hermetic package while properly accommodating the internal elements.
  • the glass lid may be a laminated glass obtained by bonding a plurality of glass plates.
  • a functional film may be formed on the surface of the glass lid on the inner element side, or a functional film may be formed on the outer surface of the glass lid.
  • an antireflection film is preferable as the functional film.
  • the thickness of the glass lid is preferably 0.1 mm or more, 0.2 to 2.0 mm, 0.4 to 1.5 mm, particularly 0.5 to 1.2 mm. If the thickness of the glass lid is small, the strength of the hermetic package is likely to decrease. On the other hand, when the thickness of the glass lid is large, it is difficult to reduce the thickness of the hermetic package.
  • the difference in thermal expansion coefficient between the glass lid and the sealing material layer is preferably less than 50 ⁇ 10 ⁇ 7 / ° C., less than 40 ⁇ 10 ⁇ 7 / ° C., and particularly preferably 30 ⁇ 10 ⁇ 7 / ° C. or less.
  • this difference in thermal expansion coefficient is too large, the stress remaining in the sealed portion becomes unreasonably high, and the hermetic reliability of the hermetic package tends to be lowered.
  • the sealing material layer is composed of the sealing material of the present invention, and is softened and deformed by absorbing laser light to form a reaction layer on the surface layer of the package substrate, and the package substrate and the glass lid are hermetically integrated. It has a function to convert.
  • the end portion (inner end portion and / or outer end portion) of the sealing material layer preferably protrudes laterally in an arc shape in a cross-sectional view, and the inner end portion and the outer end portion of the sealing material layer are circular. More preferably, it projects in an arc. This makes it difficult for the sealing material layer to be bulk broken when shearing stress is applied to the hermetic package. As a result, the airtight reliability of the airtight package can be improved.
  • the sealing material layer is preferably formed so that the contact position with the frame portion is separated from the inner edge of the top portion of the frame portion, and is separated from the outer edge of the top portion of the frame portion, More preferably, it is formed at a position 50 ⁇ m or more, 60 ⁇ m or more, 70 to 2000 ⁇ m, particularly 80 to 1000 ⁇ m apart from the inner edge of the top of the frame. If the distance between the inner edge of the top of the frame and the sealing material layer is too short, the heat generated by local heating will be difficult to escape during laser sealing, and the glass lid will be easily damaged during the cooling process. .
  • the distance between the inner edge of the top of the frame and the sealing material layer is too long, it is difficult to reduce the size of the hermetic package. Further, it is preferably formed at a position 50 ⁇ m or more, 60 ⁇ m or more, 70 to 2000 ⁇ m, particularly 80 to 1000 ⁇ m apart from the outer edge of the top of the frame portion. If the distance between the outer edge of the top of the frame and the sealing material layer is too short, the heat generated by local heating will be difficult to escape during laser sealing, and the glass lid will be easily damaged during the cooling process. . On the other hand, if the distance between the outer edge of the top of the frame and the sealing material layer is too long, it is difficult to reduce the size of the hermetic package.
  • the sealing material layer is preferably formed so that the position of contact with the glass lid is 50 ⁇ m or more, 60 ⁇ m or more, 70 to 1500 ⁇ m, particularly 80 to 800 ⁇ m away from the edge of the glass lid. If the separation distance between the edge of the glass lid and the sealing material layer is too short, the surface temperature difference between the surface on the inner element side and the outer surface of the glass lid in the edge region of the glass lid during laser sealing. It becomes large and the glass lid is easily broken.
  • the sealing material layer is preferably formed on the center line in the width direction of the top of the frame, that is, formed in the central region of the top of the frame. In this way, the heat generated by local heating is easily escaped at the time of laser sealing, so that the glass lid is difficult to break. In addition, when the width
  • the average thickness of the sealing material layer is preferably less than 8.0 ⁇ m, particularly 1.0 ⁇ m or more and less than 6.0 ⁇ m.
  • the smaller the average thickness of the sealing material layer the lower the stress remaining in the sealing portion after laser sealing when the thermal expansion coefficients of the sealing material layer and the glass lid are mismatched.
  • the accuracy of laser sealing can be increased.
  • Examples of the method for regulating the average thickness of the sealing material layer as described above include a method of thinly applying the composite powder paste, a method of polishing the surface of the sealing material layer, and the like.
  • the maximum width of the sealing material layer is preferably 1 ⁇ m or more and 2000 ⁇ m or less, 10 ⁇ m or more, 1000 ⁇ m or less, 50 ⁇ m or more and 800 ⁇ m or less, particularly 100 ⁇ m or more and 600 ⁇ m or less.
  • the maximum width of the sealing material layer is narrowed, the sealing material layer is easily separated from the edge of the frame portion, so that it is easy to reduce the stress remaining in the sealing portion after laser sealing. Furthermore, the width of the frame portion of the package substrate can be reduced, and the effective area that functions as a device can be increased.
  • the maximum width of the sealing material layer is too narrow, the sealing material layer easily breaks in bulk when a large shear stress is applied to the sealing material layer. Furthermore, the accuracy of laser sealing tends to be reduced.
  • a value obtained by dividing the average thickness of the sealing material layer by the maximum width of the sealing material layer is preferably 0.003 or more, 0.005 or more, 0.01 to 0.1, particularly 0.02 to 0.05. is there.
  • the value obtained by dividing the average thickness of the sealing material layer by the maximum width of the sealing material layer is too small, the bulk of the sealing material layer is easily broken when a large shear stress is applied to the sealing material layer.
  • the value obtained by dividing the average thickness of the sealing material layer by the maximum width of the sealing material layer is too large, the accuracy of laser sealing tends to be lowered.
  • the surface roughness Ra of the sealing material layer is preferably less than 0.5 ⁇ m, 0.2 ⁇ m or less, and particularly 0.01 to 0.15 ⁇ m. Further, the surface roughness RMS of the sealing material layer is preferably less than 1.0 ⁇ m and 0.5 ⁇ m or less, particularly 0.05 to 0.3 ⁇ m. In this way, the adhesion between the package substrate and the sealing material layer is improved, and the accuracy of laser sealing is improved.
  • the “surface roughness RMS” can be measured by, for example, a stylus type or non-contact type laser film thickness meter or surface roughness meter. Examples of the method for regulating the surface roughness Ra and RMS of the sealing material layer as described above include a method of polishing the surface of the sealing material layer, a method of reducing the particle size of the refractory filler powder, and the like. .
  • the package base and the glass lid are hermetically sealed by irradiating a laser beam from the glass lid side toward the sealing material layer and softening and deforming the sealing material layer. It is preferable to obtain an airtight package.
  • the glass lid may be disposed below the package substrate, but it is preferable to dispose the glass lid above the package substrate from the viewpoint of laser sealing efficiency.
  • a semiconductor laser a YAG laser, a CO 2 laser, an excimer laser, and an infrared laser are preferable in terms of easy handling.
  • the atmosphere for laser sealing is not particularly limited, and may be an air atmosphere or an inert atmosphere such as a nitrogen atmosphere.
  • the glass lid When performing laser sealing, if the glass lid is preheated at a temperature of 100 ° C. or higher and not higher than the heat resistance temperature of the internal element, it becomes easy to suppress breakage of the glass lid due to thermal shock during laser sealing. Further, if the annealing laser is irradiated from the glass lid side immediately after the laser sealing, it becomes easier to further suppress the breakage of the glass lid due to thermal shock or residual stress.
  • FIG. 1 is a schematic cross-sectional view for explaining an embodiment of an airtight package.
  • the hermetic package 1 includes a package base 10 and a glass lid 11.
  • the package base 10 includes a base 12 and a frame-shaped frame portion 13 on the outer peripheral edge of the base 12.
  • An internal element 14 is accommodated in the frame portion 13 of the package base 10.
  • An electrical wiring (not shown) that electrically connects the internal element 14 and the outside is formed in the package base 10.
  • the sealing material layer 15 is arranged over the entire circumference of the top of the frame 13 between the top of the frame 13 of the package base 10 and the surface of the glass lid 11 on the internal element 14 side. Moreover, the sealing material layer 15 is comprised with the sealing material of this invention.
  • the width of the sealing material layer 15 is smaller than the width of the top portion of the frame portion 13 of the package substrate 10, and is further away from the edge of the end portions of the glass lid 11 and the frame portion 13. Furthermore, the average thickness of the sealing material layer 15 is less than 8.0 ⁇ m.
  • the airtight package 1 can be manufactured as follows. First, the glass lid 11 on which the sealing material layer 15 is formed in advance is placed on the package base 10 so that the sealing material layer 15 and the top of the frame portion 13 are in contact with each other. Subsequently, the laser beam L emitted from the laser irradiation device 18 is irradiated along the sealing material layer 15 from the glass lid 11 side while pressing the glass lid 11 using a pressing jig. As a result, the sealing material layer 15 softens and flows and reacts with the top layer of the frame portion 13 of the package base 10, whereby the package base 10 and the glass lid 11 are hermetically integrated, and the airtight structure of the hermetic package 1. Is formed.
  • Table 1 shows examples of the present invention (Sample Nos. 1 to 4) and comparative examples (Sample Nos. 5 to 8).
  • “NA” means not measured.
  • the glass powder described in the table was produced as follows. First, a glass batch in which various raw materials were prepared so as to have the glass composition in the table was prepared, and this was put in a platinum crucible and melted at 900 ° C. for 1 hour. Upon melting, the mixture was stirred with a platinum rod to homogenize the molten glass. Next, a part of the obtained molten glass was poured out between water-cooled twin rollers and formed into a film shape, and the remaining molten glass was poured out into a carbon mold and formed into a rod shape.
  • the obtained glass film was pulverized with a ball mill and then classified with an air classifier so that the average particle diameter D 50 was 1.0 ⁇ m and the maximum particle diameter D max was 3.0 ⁇ m. Further, the rod-shaped glass was put into an electric furnace maintained at a temperature about 20 ° C. higher than the annealing point, and then slowly cooled to room temperature at a temperature lowering rate of 3 minutes / minute. This rod-shaped glass is used for density measurement.
  • NbZr (PO 4 ) 3 was used as the refractory filler powder.
  • the refractory filler powder is adjusted to an average particle diameter D 50 of 1.0 ⁇ m and a maximum particle diameter D max of 3.0 ⁇ m by air classification.
  • the thermal expansion coefficient ⁇ is a value measured with a TMA apparatus in a temperature range of 30 to 150 ° C.
  • a measurement sample of TMA after each sample was sintered precisely, it was processed into a predetermined shape.
  • a powder having a mass corresponding to 0.6 cm 3 minutes was dry-pressed into a button shape having an outer diameter of 20 mm using a mold, and this was placed on an alumina substrate having a thickness of 25 mm ⁇ 25 mm ⁇ 0.6 mm. Placed, heated in air at a rate of 10 ° C / minute, held at 510 ° C for 10 minutes, then cooled to room temperature at 10 ° C / minute, and measured the button diameter (flow diameter) It is evaluated by doing. Specifically, the case where the flow diameter was 16.0 mm or more was evaluated as “ ⁇ ”, and the case where it was less than 16.0 mm was evaluated as “x”.
  • the laser sealing strength was evaluated as follows. First, each sample and vehicle (tripropylene glycol monobutyl ether containing ethylcellulose resin) were uniformly kneaded with a three-roll mill and made into a paste, and then an alkali-free glass substrate (OA-10, ⁇ manufactured by Nippon Electric Glass Co., Ltd.) 40 mm ⁇ 0.5 mm thickness, thermal expansion coefficient 38 ⁇ 10 ⁇ 7 / ° C.) along the edge of the non-alkali glass substrate in a frame shape (5 ⁇ m thickness, 0.6 mm width) and 120 mm in a drying oven. Dry at 10 ° C. for 10 minutes.
  • OA-10 alkali-free glass substrate
  • the temperature was raised from room temperature at 10 ° C./minute, baked at 450 ° C. for 10 minutes, and then lowered to room temperature at 10 ° C./minute to incinerate the resin component in the paste (debinder treatment) and the sealing material Fixing was performed to form a sealing material layer on the alkali-free glass substrate.
  • an alkali-free glass substrate having a sealing material layer is accurately stacked on an LTCC package ( ⁇ 40 mm) on which no sealing material layer is formed, and then the sealing material is formed from the alkali-free glass substrate side.
  • the sealing material layer was softened and fluidized, and the alkali-free glass substrate and the LTCC package were hermetically sealed.
  • the laser light irradiation conditions (output and irradiation speed) were adjusted according to the average thickness of the sealing material layer.
  • the airtight reliability was evaluated as follows.
  • the sealing structure obtained by the above method was held for 1000 hours in a constant temperature and humidity chamber maintained at 85 ° C. and a humidity of 85%. After that, the sealing structure was observed with an optical microscope.
  • the sealing material layer did not change in quality and the invasion of moisture was not recognized in the sealing structure.
  • the airtight reliability was evaluated with “ ⁇ ” indicating that the sealing material layer was altered and “X” indicating that water had entered the sealing structure.
  • a package base having an outer dimension of 30 mm ⁇ 20 mm, a frame portion width of 2.5 mm formed along the outer shape, a frame portion height of 2.5 mm, and a base portion thickness of 1.0 mm is obtained.
  • a green sheet (MLS-26B manufactured by Nippon Electric Glass Co., Ltd.) was laminated and pressure-bonded, followed by firing at 870 ° C. for 20 minutes to obtain a package substrate made of glass ceramic.
  • Specimen no. Airtight packages according to 1 to 4 were obtained, respectively.
  • a glass lid made of borosilicate glass BDA manufactured by Nippon Electric Glass Co., Ltd., 30 mm ⁇ 20 mm ⁇ thickness 0.3 mm
  • the above sample No. A frame-shaped sealing material layer was formed using the sealing materials according to 1 to 4. More specifically, first, the sample No. 1 was adjusted so that the viscosity was about 100 Pa ⁇ s (25 ° C., Shear rate: 4). After the kneading of the sealing material according to 1 to 4, the vehicle and the solvent, the mixture was further kneaded with a three-roll mill until the powder was evenly dispersed to obtain a sealing material paste.
  • the above-mentioned sealing material paste was printed in a frame shape by a screen printer along the outer peripheral edge of the glass lid. Furthermore, after drying at 120 ° C. for 10 minutes in an air atmosphere, the sealing material layer having an average width of 400 ⁇ m and an average thickness of 6 ⁇ m is formed on the glass lid by baking at 500 ° C. for 10 minutes in the air atmosphere. Formed
  • the sealing material is irradiated from the glass lid side along the sealing material layer with a laser beam having a wavelength of 808 nm.
  • the layer is softened and fluidized, and the glass lid and the package base are hermetically sealed. Airtight packages according to 1 to 4 were obtained, respectively.
  • sample No. The airtight package according to 1 to 4 was held for 1000 hours in a constant temperature and humidity chamber maintained at 85 ° C. and 85% humidity, and then observed with an optical microscope. As a result, no moisture intrusion was observed in the sealed structure. . Therefore, sample no.
  • the hermetic packages 1 to 4 are considered to have high hermetic reliability.
  • the glass powder of the present invention and the sealing material using the glass powder are suitable for laser sealing of airtight packages such as MEMS packages and LED packages, and are solar cells such as dye-sensitized solar cells and CIGS thin film compound solar cells. It is also suitable for laser sealing.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

La poudre de verre selon la présente invention est caractérisée en ce qu'elle contient, en tant que composition de verre, en % en moles en termes d'oxydes, de 10 à 50 % d'Ag2O, pas moins de 10 % mais moins de 35 % de P2O5, pas moins de 1 % mais moins de 35 % de TeO2, plus de 3 % mais moins de 25 % de ZnO, de 0 à 10 % de Nb2O5, et de 1 à 30 % de CuO + MnO + Fe2O3 + V2O5 + NiO + WO3 + MoO3 + Co3O4.
PCT/JP2019/003769 2018-02-28 2019-02-04 Poudre de verre et matériau d'étanchéité l'utilisant Ceased WO2019167549A1 (fr)

Applications Claiming Priority (4)

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JP2018-034879 2018-02-28
JP2018034879 2018-02-28
JP2018073042A JP2019151539A (ja) 2018-02-28 2018-04-05 ガラス粉末及びそれを用いた封着材料
JP2018-073042 2018-04-05

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023086521A (ja) * 2021-12-10 2023-06-22 Ａｇｃ株式会社 ガラスペースト

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002037644A (ja) * 2000-05-16 2002-02-06 Nippon Electric Glass Co Ltd 封着用ガラス及びそれを用いた封着材料
JP2002179436A (ja) * 2000-12-14 2002-06-26 Nippon Electric Glass Co Ltd 銀リン酸系ガラス及びそれを用いた封着材料
JP2009067632A (ja) * 2007-09-13 2009-04-02 Nippon Electric Glass Co Ltd 光部品用封着ガラスおよび光部品の封着方法
JP2009256116A (ja) * 2008-04-14 2009-11-05 Nippon Electric Glass Co Ltd 封着用ガラス組成物および封着材料

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002037644A (ja) * 2000-05-16 2002-02-06 Nippon Electric Glass Co Ltd 封着用ガラス及びそれを用いた封着材料
JP2002179436A (ja) * 2000-12-14 2002-06-26 Nippon Electric Glass Co Ltd 銀リン酸系ガラス及びそれを用いた封着材料
JP2009067632A (ja) * 2007-09-13 2009-04-02 Nippon Electric Glass Co Ltd 光部品用封着ガラスおよび光部品の封着方法
JP2009256116A (ja) * 2008-04-14 2009-11-05 Nippon Electric Glass Co Ltd 封着用ガラス組成物および封着材料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023086521A (ja) * 2021-12-10 2023-06-22 Ａｇｃ株式会社 ガラスペースト
JP7757760B2 (ja) 2021-12-10 2025-10-22 Ａｇｃ株式会社 ガラスペースト

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