WO2018186200A1 - Matériau d'étanchéité et procédé de production de poudre de verre cristallisé - Google Patents

Matériau d'étanchéité et procédé de production de poudre de verre cristallisé Download PDF

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Publication number
WO2018186200A1
WO2018186200A1 PCT/JP2018/011577 JP2018011577W WO2018186200A1 WO 2018186200 A1 WO2018186200 A1 WO 2018186200A1 JP 2018011577 W JP2018011577 W JP 2018011577W WO 2018186200 A1 WO2018186200 A1 WO 2018186200A1
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Prior art keywords
sealing material
glass
material layer
glass powder
crystallized glass
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PCT/JP2018/011577
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English (en)
Japanese (ja)
Inventor
将行 廣瀬
光佑 吉田
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日本電気硝子株式会社
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Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to JP2019511154A priority Critical patent/JPWO2018186200A1/ja
Publication of WO2018186200A1 publication Critical patent/WO2018186200A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • 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

Definitions

  • the present invention relates to a sealing material and a method for producing crystallized glass powder, and more specifically to a sealing material used for laser sealing and a method for producing crystallized glass powder.
  • a composite powder material including glass powder and ceramic powder is used as the sealing material.
  • This sealing material is excellent in chemical durability and heat resistance as compared with a resin-based adhesive, and is suitable for ensuring airtightness.
  • high-expansion low-melting glass such as PbO glass or bismuth glass is used (see Patent Documents 1 and 2).
  • the thermal expansion coefficient of the sealing material can be effectively reduced.
  • the thickness of the sealing material layer In recent years, there is a demand for reducing the thickness of the sealing material layer. For example, when laser sealing (sealing by laser light irradiation) is performed, the accuracy of laser sealing can be significantly increased by reducing the thickness of the sealing material layer. Moreover, reducing the thickness of the sealing material layer can contribute to the reduction in the height and size of the display and the hermetic package.
  • the particle size of the ceramic powder in the sealing material must be reduced.
  • the ceramic powder is produced by a solid phase reaction method, it is very hard and requires a large impact and time for pulverization. Also, the solid phase reaction itself takes time. Therefore, when the ceramic powder is refined, there arises a problem that the productivity of the sealing material is greatly reduced.
  • the present invention has been made in view of the above circumstances, and its technical problem is to create a sealing material that does not decrease productivity even when the constituent material is made finer and has a low coefficient of thermal expansion. That is.
  • the sealing material of the present invention is characterized by containing at least a bismuth-based glass powder and a negatively expanded crystallized glass powder.
  • bismuth-based glass refers to a glass having a Bi 2 O 3 content of 25 mol% or more in the glass composition.
  • the negatively-expanded crystallized glass powder is produced by once forming a glass melt to obtain a crystalline glass, followed by crystallization. In this way, the glass phase remains in the crystallized glass and cracks are generated in the glass phase, so that the crystallized glass powder can be easily refined. Furthermore, negative expansion crystals such as LAS crystals can be easily precipitated. As a result, it is possible to achieve both the finer sealing material and the lower expansion without reducing the productivity.
  • the main crystal of the crystallized glass powder is ⁇ -eucryptite or ⁇ -quartz solid solution.
  • LAS-based crystals Li 2 O—Al 2 O 3 —nSiO 2
  • ⁇ -eucryptite Li 2 O—Al 2 O 3 —2SiO 2
  • ⁇ -eucryptite are further solidified from SiO 2.
  • the melted ⁇ -quartz solid solution Li 2 O—Al 2 O 3 —nSiO 2 : n> 2 has a negative expansion characteristic due to distortion of grain boundaries between crystal grains.
  • the crystallized glass powder does not substantially contain components other than SiO 2 , Al 2 O 3 , Li 2 O, TiO 2 , and ZrO 2 .
  • substantially free of components other than SiO 2 , Al 2 O 3 , Li 2 O, TiO 2 , and ZrO 2 means SiO 2 , Al 2 O 3 , Li 2 O, TiO in the composition. This refers to the case where the total content of 2 and ZrO 2 is 99.7 mol% or more.
  • the sealing material of the present invention preferably has a thermal expansion coefficient of less than 74 ⁇ 10 ⁇ 7 / ° C. in the temperature range of 30 to 300 ° C.
  • the “thermal expansion coefficient at 30 to 300 ° C.” can be measured by TMA (push bar type thermal expansion coefficient measurement).
  • the sealing material of the present invention is preferably used for laser sealing.
  • the manufacturing method of the crystallized glass powder of the present invention includes a melting step of melting a raw material batch to obtain a glass melt, a molding step of forming a glass melt to obtain a crystalline glass, and crystallizing the crystalline glass. And a crystallization step for obtaining crystallized glass and a pulverization step for pulverizing the crystallized glass to obtain a crystallized glass powder.
  • crystallized glass powder of the present invention it is preferable to crystallize the crystalline glass at a temperature of 900 to 1400 ° C.
  • the sealing material of the present invention contains at least a bismuth-based glass powder and a negatively expanded crystallized glass powder.
  • the content of crystallized glass powder in the sealing material is preferably 1 to 45% by volume, 10 to 45% by volume, 15 to 40% by volume, particularly 20 to 35% by volume.
  • content of crystallized glass powder When there is too little content of crystallized glass powder, it will become difficult to reduce the thermal expansion coefficient of a sealing material, and the mechanical strength of a sealing material layer will fall easily.
  • content of bismuth-type glass powder will become relatively small, and it will become difficult to ensure desired softening fluidity
  • ⁇ -eucryptite or ⁇ -quartz solid solution is preferably precipitated as the main crystal, and other crystals are preferably not precipitated, but the effect of the present invention is significantly impaired. Unless otherwise, a small amount of other crystals may be precipitated.
  • the crystallized glass powder has a composition of mol%, Li 2 O 10 to 35% (preferably 16 to 28%), Al 2 O 3 10 to 60% (preferably 25 to 50%), SiO 2 20 to It is preferable to contain 65% (preferably 25 to 55%) and TiO 2 + ZrO 2 0.005 to 5% (preferably 0.1 to 4%).
  • TiO 2 and ZrO 2 are components that increase the production rate of LAS-based crystals, but if their content is too large, the thermal expansion coefficient of the crystallized glass powder tends to increase.
  • the crystallized glass powder does not substantially contain components other than SiO 2 , Al 2 O 3 , Li 2 O, TiO 2 , and ZrO 2 . If a component other than SiO 2 , Al 2 O 3 , Li 2 O, TiO 2 , ZrO 2 is contained in the crystallized glass powder, the compatibility with the bismuth-based glass powder is reduced, and the bismuth-based powder is sealed at the time of laser sealing. There is a risk of devitrification of the glass. In addition, a high expansion glass phase remains in the crystallized glass powder, which may increase the thermal expansion coefficient of the crystallized glass powder. In addition, when substantially no components other than SiO 2 , Al 2 O 3 , Li 2 O, TiO 2 , and ZrO 2 are contained, the moldability and foaming properties are reduced. It doesn't matter.
  • the manufacturing method of the crystallized glass powder of the present invention includes a melting step of melting a raw material batch to obtain a glass melt, a molding step of forming a glass melt to obtain a crystalline glass, and crystallizing the crystalline glass. And a crystallization step for obtaining crystallized glass and a pulverization step for pulverizing the crystallized glass to obtain a crystallized glass powder. If it does in this way, it will become easy to refine
  • the raw material batch can be melted in an electric furnace, a gas furnace or the like.
  • the melting temperature of the raw material batch is preferably 1450 to 1650 ° C., particularly 1500 to 1600 ° C. If the melting temperature is too low, the glass melt becomes inhomogeneous and the amount of crystallized crystals of the crystallized glass powder tends to decrease. On the other hand, when the melting temperature is too high, a part of the glass component is volatilized and the glass composition tends to fluctuate.
  • the melting time of the raw material batch is preferably 1 to 3 hours. If the melting time is too short, the glass melt becomes inhomogeneous and the amount of crystallized crystals of the crystallized glass powder tends to decrease. On the other hand, if the firing time is too long, part of the glass component volatilizes and the glass composition tends to fluctuate.
  • the raw material batch is preferably mixed using a multi-mill or the like. In this way, since the uniformity of the raw material batch is improved, the glass melt is likely to be homogeneous.
  • the glass melt is preferably formed into a film. In this way, since many cracks are generated in the crystalline glass, the pulverization efficiency of the crystallized glass is improved and the crystallized glass powder is easily refined.
  • the method for producing crystallized glass powder of the present invention it is preferable to crystallize the crystalline glass at a temperature of 900 to 1400 ° C., particularly 1000 to 1300 ° C. If the crystallization temperature is too low, the formation of crystal nuclei does not proceed sufficiently, and there is a risk that many highly expanded glass phases remain. On the other hand, if the crystallization temperature is too high, the crystals melt and become a glass melt.
  • the crystallized glass can be pulverized by a ball mill, a jaw crusher, a jet mill, a disk mill, a spectro mill, a grinder, a mixer mill or the like. From this point of view, it is preferable to carry out by a wet or dry method using a ball mill. In this way, since the particle diameter of the crystallized glass powder becomes small, it can be suitably applied to an airtight package in which the sealing material layer has a small thickness.
  • Bismuth glass powder is a glass composition including, in mol%, Bi 2 O 3 28 ⁇ 60%, B 2 O 3 15 ⁇ 37%, preferably contains 1 ⁇ 30% ZnO.
  • the reason for limiting the content range of each component as described above will be described below. In the description of the glass composition range,% display indicates mol%.
  • Bi 2 O 3 is a main component for lowering the softening point, and its content is preferably 28 to 60%, 33 to 55%, particularly preferably 35 to 45%. If the content of Bi 2 O 3 is too small, too high softening point, softening fluidity tends to decrease. On the other hand, when the content of Bi 2 O 3 is too large, the glass tends to be devitrified at the time of laser sealing, and softening fluidity is likely to be lowered due to this devitrification.
  • B 2 O 3 is an essential component as a glass forming component, and its content is preferably 15 to 37%, 20 to 33%, particularly preferably 25 to 30%. If the content of B 2 O 3 is too small, it becomes difficult to form a glass network, so that the glass is easily devitrified at the time of laser sealing. On the other hand, when the content of B 2 O 3 is too large, the viscosity of the glass becomes high, the softening fluidity tends to decrease.
  • ZnO is a component that enhances thermal stability, and its content is preferably 1 to 30%, 3 to 25%, 5 to 22%, particularly preferably 9 to 20%. If the ZnO content is too low or too high, the component balance of the glass composition is impaired and the thermal stability tends to decrease.
  • SiO 2 is a component that increases water resistance, but has an action of increasing the softening point. However, if the content of SiO 2 is too large, the softening fluidity tends to decrease, and the glass tends to devitrify during laser sealing. Therefore, the content of SiO 2 is preferably 0 to 5%, 0 to 3%, 0 to 2%, particularly preferably 0 to 1%.
  • Al 2 O 3 is a component that enhances water resistance, and its content is preferably 0 to 10%, 0 to 5%, particularly preferably 0.1 to 2%. When the content of Al 2 O 3 is too large, there is a possibility that the softening point is unduly increased.
  • Li 2 O, Na 2 O and K 2 O are components that lower the thermal stability. Therefore, the contents of Li 2 O, Na 2 O and K 2 O are 0 to 5%, 0 to 3%, particularly 0 to less than 1%, respectively.
  • MgO, CaO, SrO and BaO are components that increase the thermal stability, but are components that increase the softening point. Therefore, the contents of MgO, CaO, SrO and BaO are 0 to 20%, 0 to 10%, particularly 0 to 5%, respectively.
  • the CuO content is preferably 0 to 40%, 5 to 35%, 10 to 30%, and particularly preferably 15 to 25%.
  • Fe 2 O 3 is a component that enhances thermal stability and laser absorption characteristics, and its content is preferably 0 to 10%, 0.1 to 5%, particularly preferably 0.5 to 3%. When the content of Fe 2 O 3 is too large, is impaired balance of components glass composition, thermal stability tends to decrease in reverse.
  • MnO 2 is a component that enhances laser absorption characteristics. However, when the content of MnO 2 is too large, the thermal stability tends to decrease. Therefore, the content of MnO 2 is preferably 0 to 20%, 1 to 15%, particularly 3 to 10%.
  • Sb 2 O 3 is a component that enhances thermal stability, and its content is preferably 0 to 5%, particularly preferably 0 to 2%. When the content of Sb 2 O 3 is too large, is impaired balance of components glass composition, thermal stability tends to decrease in reverse.
  • PbO is not substantially contained from an environmental viewpoint, that is, less than 0.1 mol%.
  • the sealing material of the present invention may introduce other powder materials besides glass powder and crystallized glass powder.
  • a laser absorber such as Mn—Fe—Al oxide or Mn—Fe—Cr oxide may be contained. Glass beads, spacers, etc. may be introduced.
  • a small amount of ceramic powder may be added as a thermal expansion adjusting material.
  • ceramic powder for example, cordierite, zircon, alumina, mullite, willemite, zirconium phosphate, zirconium tungstate phosphate, tungstic acid
  • the total content is preferably 0 to 15% by volume, 0 to 10% by volume, 0 to 5% by volume, particularly preferably 0 to less than 1% by volume. .
  • the average particle diameter D 50 is preferably 20 ⁇ m or less, 10 ⁇ m or less, 7 ⁇ m or less, 5 ⁇ m or less, particularly 1 to 3 ⁇ m.
  • the “average particle diameter D 50 ” refers to a value measured by the laser diffraction method. 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 diameter is 50%.
  • the maximum particle diameter D max is preferably 50 ⁇ m or less, 30 ⁇ m or less, 20 ⁇ m or less, 15 ⁇ m or less, particularly 2 to 10 ⁇ m. If the maximum particle diameter Dmax of the sealing material is too large, it is difficult to increase the accuracy of laser sealing. “Maximum particle diameter D max ” refers to a value measured by the laser diffraction method. 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 thermal expansion coefficient in the temperature range of 30 to 300 ° C. is preferably less than 74 ⁇ 10 ⁇ 7 / ° C., 73 ⁇ 10 ⁇ 7 / ° C. or less, particularly 50 ⁇ 10 ⁇ 7 / ° C. or more. And 72 ⁇ 10 ⁇ 7 / ° C. or less. If the thermal expansion coefficient is too high, it becomes difficult to ensure airtight reliability.
  • the sealing material of the present invention may be used in a powder state, but is preferably kneaded uniformly with a vehicle and made into a paste for easy handling.
  • a vehicle usually includes a solvent and a resin.
  • the resin is added for the purpose of adjusting the viscosity of the paste.
  • surfactant, a thickener, etc. can also be added as needed.
  • the produced paste is applied to the surface of an object to be sealed using an applicator such as a dispenser or a screen printer.
  • 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, water, 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), - methyl-2-pyrrolidone or the like can be used.
  • ⁇ -terpineol is preferable because of its high viscosity
  • the sealing material of the present invention is preferably used for sealing 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. If it does in this way, it will become easy to accommodate internal elements, such as 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. Further, it becomes easy to accommodate internal elements such as LED elements in the frame portion of the package base, and it is 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. Glass ceramic has the 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., 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 decrease.
  • 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.
  • the glass melt was poured between forming rollers (double rollers) to rapidly cool the glass melt and to form a film shape. Subsequently, the glass film was crystallized at the crystallization temperature and crystallization time described in Table 1.
  • the obtained crystallized glass film was pulverized by dry pulverization and wet pulverization until the average particle diameter D 50 became 1.0 ⁇ m, and then classified by a 350 mesh test sieve. Crystallized glass powders according to 1 to 7 were obtained.
  • the obtained sealing material was fired at 500 ° C. to obtain a dense fired body, and then the fired body was processed into a predetermined shape to prepare a measurement sample for TMA. Using this measurement sample, TMA was performed in the temperature range of 30 to 300 ° C., and the thermal expansion coefficient of the sealing material was calculated. The results are shown in Table 1.
  • the thermal stability is evaluated by visually observing the surface of the fired body and evaluating as “ ⁇ ” when crystals are not precipitated and as “X” when crystals are precipitated.
  • sample no. Nos. 1 to 6 had good thermal stability. Therefore, sample no. 1 to 6 are considered suitable for the sealing material.
  • Sample No. The crystallized glass powders according to Nos. 1 and 2 were crystallized at 1000 ° C. substantially free of components other than SiO 2 , Al 2 O 3 , Li 2 O, TiO 2 and ZrO 2 in the composition.
  • Sample No. The crystallized glass powder according to No. 3 was crystallized at 1300 ° C. substantially free of components other than SiO 2 , Al 2 O 3 , and Li 2 O in the composition.
  • sample no. 1 to 3 had a thermal expansion coefficient of 72 ⁇ 10 ⁇ 7 / ° C. or less.
  • the crystallized glass powders according to 4 to 5 substantially contain components other than SiO 2 , Al 2 O 3 , Li 2 O, TiO 2 and ZrO 2 in the composition. Since the crystallized glass powder according to No. 6 had a crystallization temperature of less than 900 ° C., each had a thermal expansion coefficient of 75 ⁇ 10 ⁇ 7 / ° C. or more.

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  • Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)

Abstract

L'invention concerne un matériau d'étanchéité caractérisé en ce qu'il comprend au moins une poudre de verre à base de bismuth et une poudre de verre cristallisé d'expansion négative.
PCT/JP2018/011577 2017-04-06 2018-03-23 Matériau d'étanchéité et procédé de production de poudre de verre cristallisé WO2018186200A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001172048A (ja) * 1998-10-23 2001-06-26 Ohara Inc 負熱膨張性ガラスセラミックスおよびその製造方法
JP2002104841A (ja) * 2000-09-28 2002-04-10 Ohara Inc ガラスセラミックス及び温度補償部材
JP2007091577A (ja) * 2005-09-05 2007-04-12 Ohara Inc 無機物粉末およびそれを用いた複合体
WO2012090943A1 (fr) * 2010-12-27 2012-07-05 旭硝子株式会社 Elément de verre avec une couche de matériau d'étanchéité, dispositif électronique utilisant ledit élément de verre et procédé de production dudit élément de verre

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5486253B2 (ja) * 2008-10-31 2014-05-07 株式会社オハラ ガラスおよび結晶化ガラス
JP5771183B2 (ja) * 2010-02-27 2015-08-26 株式会社オハラ ガラスセラミックス、その製造方法及びその利用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001172048A (ja) * 1998-10-23 2001-06-26 Ohara Inc 負熱膨張性ガラスセラミックスおよびその製造方法
JP2002104841A (ja) * 2000-09-28 2002-04-10 Ohara Inc ガラスセラミックス及び温度補償部材
JP2007091577A (ja) * 2005-09-05 2007-04-12 Ohara Inc 無機物粉末およびそれを用いた複合体
WO2012090943A1 (fr) * 2010-12-27 2012-07-05 旭硝子株式会社 Elément de verre avec une couche de matériau d'étanchéité, dispositif électronique utilisant ledit élément de verre et procédé de production dudit élément de verre

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