WO2023106269A1 - Composition de vitrocéramique - Google Patents

Composition de vitrocéramique Download PDF

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Publication number
WO2023106269A1
WO2023106269A1 PCT/JP2022/044792 JP2022044792W WO2023106269A1 WO 2023106269 A1 WO2023106269 A1 WO 2023106269A1 JP 2022044792 W JP2022044792 W JP 2022044792W WO 2023106269 A1 WO2023106269 A1 WO 2023106269A1
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Prior art keywords
glass
ceramic composition
less
reflectance
mass
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PCT/JP2022/044792
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English (en)
Japanese (ja)
Inventor
まりな 熊谷
広修 熊岡
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Ａｇｃ株式会社
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Publication of WO2023106269A1 publication Critical patent/WO2023106269A1/fr

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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
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00—Semiconductor lasers
    • H01S5/02—Structural details or components not essential to laser action
    • H01S5/022—Mountings; Housings
    • H01S5/0225—Out-coupling of light
    • H01S5/02257—Out-coupling of light using windows, e.g. specially adapted for back-reflecting light to a detector inside the housing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00—Semiconductor lasers
    • H01S5/02—Structural details or components not essential to laser action
    • H01S5/022—Mountings; Housings
    • H01S5/023—Mount members, e.g. sub-mount members
    • H01S5/02315—Support members, e.g. bases or carriers

Definitions

  • the present invention relates to glass-ceramic compositions.
  • LEDs light emitting diodes
  • LEDs light emitting diodes
  • the LED chip is placed on a flat substrate such as aluminum nitride, and a resin-based member is used. A sealed configuration is often used.
  • GCHP registered trademark
  • Glass Ceramics Hybrid Package Glass Ceramics Hybrid Package
  • the light reflected by the cavity may affect the emitted light, causing stray light.
  • the light emitted from the light emitting element 3 when the light emitted from the light emitting element 3 is the light h ⁇ perpendicular to the main surface of the substrate 1, the light h ⁇ should be transmitted without being attenuated. is desired.
  • the light emitted from the light emitting element 3 is light h ⁇ ' that is not perpendicular to the main surface of the substrate 1, it is desirable to reduce the reflectance of the substrate 1 to absorb such light h ⁇ '. .
  • the light source when looking at the light source from the headlights of a car, the light source is very dazzling (glare) and can cause discomfort to the eyes. For this reason, for example, in a low-beam headlight, while ensuring a certain amount of light emitted toward the front of the light source, reflected light emitted toward directions other than the front of the light source is suppressed, and the light beam direction It is required to obtain light with little variation and high directivity. Such characteristics are required not only for automobile headlights but also for projectors and the like.
  • Patent Document 1 a substrate body made of a sintered body of a glass ceramic composition containing a glass powder and a ceramic filler and having a light emitting element mounting portion, and a region surrounding the light emitting element mounting portion of the substrate body and a light absorbing layer for absorbing light emitted from the light emitting element, wherein the light absorbing layer is made of a glass powder sintered body containing a light absorbing material.
  • a substrate is disclosed. As a result, the amount of reflected light on the substrate surface is reduced, and the directivity of the obtained light can be improved.
  • the strength of the obtained glass-ceramic composition decreases when trying to lower the reflectance of the fired glass-ceramic composition by adding a pigment to the glass-ceramic.
  • an object of the present invention is to provide a glass-ceramic composition that maintains a low reflectance while suppressing a decrease in strength.
  • the present inventor newly found that voids are generated by the addition of inorganic pigments and heat treatment, and that such voids are a factor in reducing the strength of the glass-ceramic composition.
  • the reflectance is 32% or less
  • the reflectance at a wavelength of 1550 nm is 25% or less
  • the porosity is 10% or less
  • the inorganic pigment is a Cr-based oxide, an Fe-based oxide, a Co-based oxide
  • the content of Al 2 O 3 in the glass-ceramic composition, which contains a composite oxide containing at least one selected from the group consisting of Mn-based oxides and Cu-based oxides, is expressed in mass %
  • a glass-ceramic composition, wherein the residual carbon content of the glass-ceramic composition is 20 mass ppm or less, which is greater than the content of the glass matrix
  • the glass matrix is made of borosilicate glass, and contains 35 to 50% by mass of the borosilicate glass, 45 to 60% by mass of the Al 2 O 3 , and 3 to 10% by mass of the inorganic pigment.
  • the glass-ceramic composition according to the present invention it is possible to suppress a decrease in strength while maintaining a low reflectance. Therefore, when the glass-ceramic composition is used as a substrate for mounting a light-emitting diode element or a semiconductor laser element, the directivity of the obtained light can be enhanced by suppressing stray light while satisfying the required strength. .
  • FIG. 1 is a schematic cross-sectional view of a common substrate on which light emitting elements are mounted.
  • FIG. 2 is a schematic cross-sectional view showing an example of the structure of a hermetically sealed package using the glass-ceramic composition according to this embodiment.
  • the glass-ceramic composition according to this embodiment is a fired body containing a glass matrix, Al 2 O 3 (alumina) and an inorganic pigment.
  • the glass-ceramic composition comprises a glass-ceramic in which Al 2 O 3 is dispersed as a filler component in a glass matrix, and an inorganic pigment is further included.
  • the optical properties of the glass-ceramic composition are such that the average reflectance in the wavelength range of 800 to 880 nm is 30% or less, the reflectance in the entire wavelength range of 900 to 910 nm is 32% or less, and the reflection at a wavelength of 1550 nm. rate is 25% or less.
  • Inorganic pigments include composite oxides containing at least one selected from the group consisting of Cr-based oxides, Fe-based oxides, Co-based oxides, Mn-based oxides, and Cu-based oxides. Inclusion of such an inorganic pigment can reduce the reflectance of the glass-ceramic composition.
  • the porosity of the glass-ceramic composition is 10% or less. This suppresses a decrease in the strength of the glass-ceramic composition. Moreover, the porosity can be reduced by lowering the residual carbon content of the glass-ceramic composition.
  • the residual carbon content in the glass-ceramic composition of the present embodiment is 20 mass ppm or less.
  • the wavelength of 800 to 880 nm is the IR wavelength region, and the average reflectance of the glass-ceramic composition in this region is 30% or less, preferably 5 to 30%, more preferably 5 to 27%. , 5 to 25% is more preferred.
  • the average reflectance is preferably 27% or less, more preferably 25% or less.
  • the lower limit of the average reflectance is not particularly limited, and the lower one is preferable, but it is usually 5% or more.
  • a wavelength of 900 to 910 nm is a wavelength range for semiconductor laser applications, and the reflectance of the glass-ceramic composition in the entire wavelength range is 32% or less, and the reflectance is preferably 5 to 32%, more preferably 5 to 30%. is more preferred, and 5 to 27% is even more preferred.
  • the reflectance is preferably 30% or less, more preferably 27% or less.
  • the lower limit of the reflectance is not particularly limited, and the lower one is preferable, but it is usually 5% or more.
  • a wavelength of 1550 nm is a wavelength range for semiconductor laser applications, and the reflectance of the glass-ceramic composition at this wavelength is 25% or less, preferably 5 to 25%, more preferably 2 to 22%, 2 to 20% is more preferred.
  • the reflectance is preferably 22% or less, more preferably 20% or less.
  • the lower limit of the reflectance is not particularly limited, and the lower one is preferable, but it is usually 5% or more.
  • the glass ceramic composition preferably has a reflectance of 5 to 25%, more preferably 5 to 20%, in the entire wavelength range of 780 to 800 nm.
  • the reflectance is preferably 25% or less, more preferably 20% or less, and the lower limit is not particularly limited, and is preferably 5% or more.
  • the glass ceramic composition preferably has a reflectance of 5 to 25%, more preferably 5 to 22%, in the entire wavelength range of 800 to 820 nm.
  • the reflectance is preferably 25% or less, more preferably 22% or less, and the lower limit is not particularly limited, and is preferably 5% or more.
  • the glass ceramic composition preferably has a reflectance of 5 to 30%, more preferably 5 to 25%, in the entire wavelength range of 820 to 840 nm.
  • the reflectance is preferably 30% or less, more preferably 25% or less, and the lower limit is not particularly limited, and is preferably 5% or more.
  • the glass ceramic composition preferably has a reflectance of 5 to 30%, more preferably 5 to 25%, in the entire wavelength range of 840 to 860 nm.
  • the reflectance is preferably 30% or less, more preferably 25% or less, and the lower limit is not particularly limited, and is preferably 5% or more.
  • the glass ceramic composition preferably has a reflectance of 5 to 32%, more preferably 5 to 25%, in the entire wavelength range of 860 to 880 nm.
  • the reflectance is preferably 32% or less, more preferably 25% or less, and the lower limit is not particularly limited, and is preferably 5% or more.
  • the glass ceramic composition preferably has a reflectance of 5 to 30%, more preferably 5 to 27%, in the entire wavelength range of 800 to 880 nm.
  • the reflectance is preferably 30% or less, more preferably 27% or less, and the lower limit is not particularly limited, and is preferably 5% or more.
  • the content of the glass matrix in the glass-ceramic composition, the content of Al 2 O 3 as a filler component in the glass-ceramic composition, and the content of the inorganic pigment in the glass-ceramic composition were all measured by cross-sectional scanning of the glass-ceramic composition. It is a value measured from a type electron microscope (SEM) image. Specifically, a cross-sectional SEM image taken at a magnification of 2000 times is binarized using image analysis software (ImageJ, manufactured by the National Institutes of Health, USA), and the glass matrix and Al 2 O 3 particles are obtained. , and the cross-sectional area of each of the inorganic pigments, and the volume % is obtained from the ratio to the sum of these, and then calculated as mass % by conversion of specific gravity.
  • SEM type electron microscope
  • the porosity of the glass-ceramic composition is 10% or less, preferably 1-10%, more preferably 1-5%, even more preferably 1-3%.
  • the porosity is preferably 5% or less, more preferably 3% or less.
  • the porosity is preferably 1% or more.
  • the porosity of the glass-ceramic composition is a value measured from a cross-sectional scanning electron microscope (SEM) image of the glass-ceramic composition.
  • a cross-sectional SEM image taken at a magnification of 500 times is subjected to binarization processing using image analysis software (ImageJ, manufactured by the National Institutes of Health, USA), and the area of the void is the total area. It is a value calculated by dividing
  • Porosity can be reduced by reducing the residual carbon content of the glass-ceramic composition.
  • a residual carbon content is thought to be derived from, for example, the carbon content contained in the inorganic pigment and the resin and solvent contained in the green sheet, which will be described later. Therefore, it is preferable to use an inorganic pigment with a low carbon content.
  • the residual carbon content in the glass-ceramic composition is 20 mass ppm or less, preferably 5 to 20 mass ppm, more preferably 5 to 18 mass ppm, even more preferably 5 to 16 mass ppm.
  • the residual carbon content is preferably 18 mass ppm or less, more preferably 16 mass ppm or less.
  • the lower limit of the residual carbon content is not particularly limited, it is preferably 5 ppm by mass or more from the viewpoint of the cost of cleaning the raw material pigment.
  • the XY shrinkage during firing means the degree of sintering of the green sheet before and after firing. Therefore, the XY shrinkage rate is preferably 14 to 17%, more preferably 14.5 to 16.5%, even more preferably 15 to 16%. Here, the XY shrinkage rate is preferably 14% or more, more preferably 14.5% or more, and even more preferably 15% or more. From the viewpoint of moldability, the XY shrinkage rate is preferably 17% or less, more preferably 16.5% or less, and even more preferably 16% or less. As the XY shrinkage, values obtained by measuring the XY dimensions of the glass-ceramic composition before and after firing using a vernier caliper are used.
  • the average density of the glass-ceramic composition is preferably 2.8 to 3.8, more preferably 2.9 to 3.7, even more preferably 3.0 to 3.6.
  • the average density is preferably 2.8 or higher, more preferably 2.9 or higher, and even more preferably 3.0 or higher.
  • the average density is preferably 3.8 or less, more preferably 3.7 or less, and even more preferably 3.6 or less.
  • a value of apparent specific gravity calculated using an electronic hydrometer is used.
  • the average strength of the glass-ceramic composition is preferably 250-400 MPa, more preferably 290-390 MPa, even more preferably 300-380 MPa.
  • the average strength is preferably 250 MPa or higher, more preferably 290 MPa or higher, and even more preferably 300 MPa or higher.
  • the average strength is preferably 400 MPa or less, more preferably 390 MPa or less, and even more preferably 380 MPa or less.
  • Autograph manufactured by Shimadzu Corporation, Autograph AGS-X
  • the inorganic pigment includes a composite oxide containing at least one selected from the group consisting of Cr-based oxides, Fe-based oxides, Co-based oxides, Mn-based oxides, and Cu-based oxides. Inclusion of such an inorganic pigment can reduce the reflectance of the glass-ceramic composition. In addition, from the viewpoint of achieving a lower reflectance, the inorganic pigment preferably exhibits a blackish or brownish hue, and more preferably exhibits a blackish hue.
  • a composite oxide of the above oxides is used as the inorganic pigment, it is easy to effectively obtain a pigment having a blackish or brownish tint.
  • a pigment having a black tint it preferably contains Mn or Fe.
  • Mn or Fe when a pigment having a blackish or brownish tint is used, it is preferable to contain Co, Cu, or Cr instead of Mn or Fe, or in addition to Mn or Fe.
  • other elements may be contained within a range that does not impair the effects of the present invention. Other elements include, for example, Zn, Ti, Mg, Ni, V, and the like.
  • the content of the residual carbon in the oxide which is an inorganic pigment, may vary depending on the composition of the oxide and the manufacturing method. For example, when there is a step of wet pulverization as a refining process in the manufacturing process, the residual carbon content tends to be low. Therefore, even if the inorganic pigments have the same composition, the inorganic pigments that have undergone wet pulverization are preferable.
  • the inorganic pigment has a residual carbon content of preferably 50 mass ppm or less, more preferably 40 mass ppm or less, even more preferably 30 mass ppm or less after heat treatment at 900°C for 12 hours, and the lower the better.
  • salts contained in the above oxides, which are inorganic pigments, in the order of impurities can also affect the porosity of the glass-ceramic composition.
  • NOx when nitrates are included as residual salts, NOx may be generated, and when sulfates are included as residual salts, SOx may be generated. Due to the generated gases such as NOx and SOx, voids were formed during the production of the glass-ceramic composition, and there was a tendency for the porosity of the glass-ceramic composition to increase.
  • the content of each of nitrate and sulfate in the inorganic pigment is preferably 300 mass ppm or less, more preferably 200 mass ppm or less, and even more preferably 100 mass ppm or less.
  • the total content of nitrates and sulfates is preferably 500 mass ppm or less, more preferably 400 mass ppm or less, and even more preferably 200 mass ppm or less.
  • the contents of the nitrates and sulfates can be obtained by determining the elution amount ( ⁇ g/g) of NO 3 - and SO 4 2- using anion chromatography and converting the values into parts per million. is the value obtained.
  • the extraction solvent in ICP emission spectrometry may be either pure water or a weak acid such as nitric acid diluted to pH 2.
  • the content of K and Na is preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less, and even more preferably 80 ppm by mass or less.
  • the total content thereof is preferably 400 mass ppm or less, more preferably 300 mass ppm or less, and even more preferably 200 mass ppm or less.
  • the total content of inorganic pigments in the glass-ceramic composition is preferably 3-10% by mass, more preferably 4-10% by mass, and even more preferably 6-10% by mass.
  • the total content of inorganic pigments is preferably 3% by mass or more, more preferably 4% by mass or more, and even more preferably 6% by mass or more.
  • the total content of inorganic pigments is preferably 10% by mass or less.
  • the composition of the glass matrix is not particularly limited, it is preferably made of amorphous glass containing no crystal phase from the viewpoint of suppressing warping of the substrate. Among them, for example, it is more preferable from the viewpoint of acid resistance to use borosilicate-based glass with a low content of Li 2 O, Na 2 O and K 2 O, which are alkali components.
  • the composition of the borosilicate glass is not particularly limited, it may contain, for example, RO, R′ 2 O 3 , ZrO 2 and the like in addition to SiO 2 and B 2 O 3 .
  • R is at least one selected from the group consisting of Zn, Ba, Sr, Mg and Ca.
  • R' is at least one selected from the group consisting of Al, Fe, Gd and La.
  • Al 2 O 3 when R′ is Al is clearly distinguished from aluminum oxide as a filler component constituting the glass-ceramic composition. That is, the Al 2 O 3 content as the glass composition is excluded from the content of the crystalline powder containing aluminum oxide as the filler component.
  • Borosilicate glass preferably contains Al 2 O 3 and CaO in addition to SiO 2 and B 2 O 3 . More specifically, for example, it contains 45 to 65% by mass of SiO 2 , 5 to 20% by mass of B 2 O 3 , 5 to 25% by mass of Al 2 O 3 , 10 to 35% by mass of CaO, and Li A glass that does not contain 2 O, Na 2 O and K 2 O or has a total content of Li 2 O, Na 2 O and K 2 O of less than 3.5 mass % is preferably used.
  • Boron oxide (B 2 O 3 ) is a component that improves the sinterability of glass, and its content in the glass matrix is preferably 5 to 20% by mass, more preferably 6 to 15% by mass, and more preferably 7 to 11% by mass. more preferred.
  • the content of boron oxide is preferably 5% by mass or more, more preferably 6% by mass or more, and even more preferably 7% by mass or more.
  • the boron oxide content is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 11% by mass or less.
  • SiO2 is a constituent of glass.
  • the component represented by RO containing CaO is a component that lowers the melting temperature of the glass and improves the sinterability.
  • crystals typified by anorthite SiO 2 —Al 2 O 3 —CaO
  • the component represented by R′ 2 O 3 including Al 2 O 3 is a component that has an effect of stabilizing the glass, suppressing crystallization, and improving the chemical durability of the glass. On the other hand, if it is added excessively, crystals typified by anorthite may precipitate during firing, making the sintered body more likely to warp, and the acid resistance may not be sufficient.
  • the component represented by ZrO2 is a component that improves the chemical durability of glass. On the other hand, if it is added excessively, the sinterability may deteriorate.
  • the content of the glass matrix in the glass-ceramic composition is preferably 30-50% by mass, more preferably 33-45% by mass, even more preferably 35-42% by mass. From the viewpoint of obtaining a dense sintered body, the content of the glass matrix is preferably 30% by mass or more, more preferably 33% by mass or more, and even more preferably 35% by mass or more. From the viewpoint of obtaining a sintered body with high strength, the content of the glass matrix is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 42% by mass or less. Moreover, when the glass matrix is made of borosilicate glass, the content of the borosilicate glass in the glass-ceramic composition is preferably within the above range.
  • the glass softening point Ts of the glass matrix is preferably 700-900°C, more preferably 750-870°C, even more preferably 800-850°C.
  • the glass softening point Ts of the glass matrix is preferably 900° C. or lower, more preferably 870° C. or lower, and even more preferably 850° C. or lower, because it is co-fired with Ag.
  • the glass softening point Ts of the glass matrix is preferably 700° C. or higher, more preferably 750° C. or higher, and even more preferably 800° C. or higher, from the viewpoint of suppressing an increase in residual carbon content.
  • the glass softening point Ts of the glass matrix is a value determined by the fourth inflection point of the DTA chart of the glass alone.
  • the glass transition point Tg of the glass matrix is preferably 700°C or lower, more preferably 680°C or lower, and even more preferably 650°C or lower so as not to inhibit thermal decomposition of the resin component.
  • the glass transition point Tg of the glass matrix is a value determined by the first inflection point of the DTA chart of the glass alone.
  • Al 2 O 3 in the glass-ceramic composition is included as a filler component.
  • the filler component in addition to Al 2 O 3 , is at least one selected from the group consisting of zirconium oxide, titanium oxide, magnesium oxide, silicon dioxide, zirconium phosphate, ⁇ -eucryptite (LiAlSiO 4 ) and mixtures thereof. It may further contain a crystalline powder containing.
  • Al 2 O 3 includes ⁇ -alumina type, ⁇ -alumina type, ⁇ -alumina type, ⁇ -alumina type, etc., depending on the type of crystal phase. preferable.
  • the content of Al 2 O 3 as a filler component in the glass-ceramic composition is preferably 40 to 60% by mass, more preferably 42 to 59% by mass, even more preferably 45 to 58% by mass.
  • the content of Al 2 O 3 is preferably 40% by mass or more, more preferably 42% by mass or more, and even more preferably 45% by mass or more.
  • the content of Al 2 O 3 is preferably 60% by mass or less, more preferably 59% by mass or less, and even more preferably 58% by mass or less.
  • the total content of the other filler components is preferably 3% by mass or less from the viewpoint of obtaining good sinterability, and 2% by mass or less. more preferred.
  • the content of Al 2 O 3 is higher than the content of the glass matrix. This is preferable because a dense sintered body having high strength can be obtained.
  • the ratio of the content of Al 2 O 3 to the content of the glass matrix is preferably 58:36 to 47.5:46.5, more preferably 54:42 to 47, in terms of Al 2 O 3 :glass matrix. .5:46.5 is more preferred, and 52:42 to 47.5:46.5 are even more preferred.
  • the shape of the Al 2 O 3 crystal powder which is the filler component, is not particularly limited and may be spherical, flat, scaly, fibrous, or the like. Similarly, when other filler components are included, the shape of the crystalline powder of the other filler components is not particularly limited.
  • the size of the crystal powder is not particularly limited, for example, the 50% particle size (D 50 ) is preferably 0.5 to 4 ⁇ m, more preferably 1 to 3 ⁇ m.
  • the 50% particle size is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, and preferably 4 ⁇ m or less, more preferably 3 ⁇ m or less.
  • the 50% particle size is a value measured using a laser diffraction/scattering particle size distribution analyzer.
  • the glass-ceramic composition according to this embodiment is preferably used as a substrate for mounting a light-emitting diode element or a semiconductor laser element.
  • a substrate preferably has a base portion and a frame portion from the viewpoint of hermetic sealing.
  • the base and the frame may be formed of the glass-ceramic composition, or the base and the frame may be formed of the flat glass and the glass-ceramic composition, respectively.
  • the substrate on which the light-emitting diode element or the semiconductor laser element is mounted is, for example, a backlight of a liquid crystal display, a light-emitting part in an operation button of a small information terminal, lighting for automobiles or decoration, a deep ultraviolet light LED for sterilization, etc. , a laser unit of a 3D ranging sensor, and other light sources.
  • the above-mentioned substrate is equipped with a system that can detect cracks in the glass because of its intended use.
  • the base has a conductive film on at least a partial region thereof
  • the frame has a metal conductor that penetrates therethrough, and that the conductive film and the metal conductor are electrically connected.
  • the metal conductor is preferably silver from the viewpoint of being able to be fired simultaneously with the glass-ceramic composition and having high heat dissipation.
  • the glass-ceramic composition according to the present embodiment has a low porosity of 10% or less and is excellent in strength, so it is also suitable as a hermetically sealed package.
  • other than optical elements such as light emitting diode elements and semiconductor laser elements, it may be used as a package that houses electronic components that require hermetic sealing by sealing them with air, nitrogen, or the like.
  • an electronic component that requires hermetic sealing is an all-solid-state battery.
  • all-solid-state batteries two types of electrolytes, an oxide-based solid electrolyte and a sulfide-based solid electrolyte, are mainly used, and the latter in particular is known to react with moisture to generate toxic gas.
  • high water resistance is required, and a package that can be hermetically sealed may be required.
  • FIG. 2 shows a schematic cross-sectional view as an example of the structure of a hermetically sealed package using the glass-ceramic composition according to this embodiment.
  • the hermetically sealed package 100 includes at least a substrate 10 made of the glass-ceramic composition according to the present embodiment, a lid portion 20, and an electronic component 30. Electrodes 12 and internal wirings 13 are provided on the surface and inside of the substrate 10 to enable electrical connection with the electronic component 30 .
  • the material of the lid portion 20 is not particularly limited as long as it can hermetically seal the electronic component 30, and may be, for example, the glass-ceramic composition according to the present embodiment, a metal material, or a translucent material.
  • the lid portion 20 is made of a light-transmitting material, it is possible to visually determine the appearance, electrode polarity, etc. of the components housed in the airtightly sealed package 100 .
  • the method of sealing the substrate 10 and the lid portion 20 is not particularly limited as long as it can be airtightly sealed, but for example, a method using metal bonding can be used. Specifically, the first metal layer 11 and the second metal layer 21 are formed on the substrate 10 and the lid portion 20 respectively, and then these are sealed using the sealing layer 40 .
  • Examples of metals used for the first metal layer 11 and the second metal layer 21 include silver (Ag), copper (Cu), and gold (Au), and these are used alone or in combination of two or more.
  • Ag is preferable in that it can be fired simultaneously with a general glass-ceramic composition including the glass-ceramic composition according to the present embodiment.
  • a protective metal film may be provided on the outermost surface of the first metal layer 11 or the second metal layer 21 , that is, the surface facing the substrate 10 or the lid portion 20 .
  • the protective metal film include gold (Au), nickel (Ni), palladium (Pd), platinum (Pt), and the like, and these are used alone or in combination of two or more.
  • sealing layer 40 for example, a sealing metal preform or solder may be used.
  • Au, tin (Sn), antimony (Sb), Ag, Ni, Pt, or alloys of these metals may be used as the metal preform for sealing. Seam sealing may be performed when forming the sealing layer 40 .
  • a glass-ceramic composition is obtained by sintering by molding and firing a mixture of glass powder, a filler component containing Al 2 O 3 and an inorganic pigment. Specifically, there is a method of forming the above mixture into a sheet called a green sheet and firing the sheet.
  • each raw material is blended so as to obtain a desired glass composition, and the mixed raw material mixture is melted, cooled, and pulverized to obtain a glass powder.
  • the glass powder obtained by grinding becomes the glass matrix and determines the glass composition of the glass-ceramic composition.
  • the melting temperature of the raw material mixture is preferably, for example, 1200 to 1600° C. or higher, and the melting time is preferably, for example, 30 to 60 minutes.
  • Pulverization may be a dry pulverization method or a wet pulverization method. In the wet pulverization method, water, ethanol, or the like can be used as a solvent.
  • pulverizers such as roll mills, ball mills, and jet mills can be used.
  • the 50% particle diameter (D 50 ) is preferably 0.5 to 4 ⁇ m, more preferably 1 to 3 ⁇ m.
  • the 50% particle size (D 50 ) is preferably 0.5 ⁇ m or more from the viewpoint of preventing the glass powder from agglomerating and making it difficult to handle, and from the viewpoint of preventing the time required for pulverization from becoming longer. 1 ⁇ m or more is more preferable.
  • the 50% particle size (D 50 ) is preferably 4 ⁇ m or less, more preferably 3 ⁇ m or less.
  • the maximum particle size of the glass powder is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, from the viewpoints of obtaining good sinterability and preventing a decrease in reflectance due to undissolved components remaining in the sintered body.
  • the particle size can be adjusted by, if necessary, classifying after pulverization.
  • the glass powder and filler components are then mixed.
  • the filler component may contain Al 2 O 3 crystal powder, and may further contain other filler components such as cordierite powder and zirconium phosphate powder, but the total amount of the other filler components may be The content is preferably 3% by mass or less.
  • the inorganic pigment may be mixed together when the glass powder and the filler component are mixed, or may be mixed after the glass powder and the filler component are mixed.
  • an organic solvent, a plasticizer, a binder, a dispersant, and the like are blended as necessary to prepare a slurry or paste.
  • Conventionally known materials can be applied to each material to be blended.
  • organic solvents include alcohols, ketones, aromatic hydrocarbons, and the like. More specifically, toluene, methyl ethyl ketone, methanol, 2-butanol, xylene and the like can be used, and these may be used alone or in combination of two or more.
  • the plasticizer include adipic acid-based and phthalic acid-based plasticizers.
  • bis(2-ethylhexyl) adipate, dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate and the like can be used.
  • a thermally decomposable resin etc. are mentioned as a binder. More specifically, acrylic resin, polyvinyl butyral, etc. can be used.
  • dispersants include surfactant-type dispersants. More specifically, DISPERBYK180 (trade name, manufactured by BYK-Chemie) or the like can be used.
  • a green sheet is obtained by applying the obtained slurry or paste on the film and drying it.
  • the thickness of the green sheet is not particularly limited, and can be adjusted by the thickness at the time of application, slurry concentration, and the like.
  • the obtained green sheets are laminated according to the desired height and molded appropriately. At this time, a mold or the like may be used instead of the green sheet for molding.
  • the green sheets may be produced one by one according to the desired shape, but by producing a large green sheet and punching it at multiple locations with a hole puncher, etc., it is possible to obtain a large number of substrates by connecting a plurality of substrates. may be used as a connecting substrate. By dividing this connecting substrate after firing, individual substrates made of the glass-ceramic composition can be obtained.
  • a conductive film, a metal conductor, or the like may be provided on such a substrate by a conventionally known method.
  • the glass-ceramic composition according to the present embodiment may be used as a frame to be joined to a base made of flat glass.
  • the glass-ceramic composition according to the present embodiment can be used as a light-emitting diode element or a semiconductor laser element together with a wiring conductor such as a conductive film or a metal conductor, even if it is not a ferrite-embedded glass-ceramic composition containing ferrite crystals in the green sheet. It is suitable for use as a substrate for mounting.
  • Degreasing may be performed as necessary, preferably at 400-550°C, for example.
  • the degreasing time is preferably 1 to 10 hours, for example.
  • the firing temperature varies depending on the glass composition constituting the glass matrix, but is preferably 850 to 905°C, more preferably 860 to 900°C, and even more preferably 870 to 890°C.
  • the firing temperature is preferably 850° C. or higher, more preferably 860° C. or higher, and even more preferably 870° C. or higher.
  • the temperature during firing should be adjusted from the viewpoint of preventing the metal such as silver from softening or melting during firing, which may prevent the shape of the wiring pattern or through conductor from being maintained. is preferably 905° C. or lower, more preferably 900° C. or lower, and even more preferably 890° C. or lower.
  • the baking time is preferably 10 to 60 minutes, more preferably 15 to 55 minutes, even more preferably 25 to 50 minutes.
  • the firing time is preferably 10 minutes or longer, more preferably 15 minutes or longer, and even more preferably 25 minutes or longer.
  • the baking time is preferably 60 minutes or less, more preferably 55 minutes or less, and even more preferably 50 minutes or less.
  • Examples 1 to 4 are working examples, and examples 5 to 7 are comparative examples.
  • the obtained glass powder, alumina powder (manufactured by Sumitomo Chemical Co., Ltd., trade name: ALM-41-01), and an inorganic pigment were blended in the ratio shown in Table 1 and mixed to obtain a glass-ceramic composition.
  • obtained the precursor of the product Details of the pigments are as shown in Table 2.
  • blanks in Table 1 mean that they are not blended.
  • a hole with a diameter of 0.17 mm was made in the green sheet using a hole puncher. Square holes with sides of 0.82 mm and 1.2 mm were formed using a hole puncher. These holes were filled with silver paste by screen printing. Further, a wiring pattern was printed on the green sheet by a screen printing method. These green sheets were then laminated. This was held at 550° C. for 5 hours for degreasing, and further held at 870° C. for 60 minutes for firing to obtain a glass-ceramic composition. The size of one piece of glass-ceramic composition was 3.1 ⁇ 2.6 mm.
  • Maximum reflectance, maximum reflectance in the entire wavelength range from 840 to 860 nm, maximum reflectance in the entire wavelength range from 860 to 880 nm, maximum reflectance in the entire wavelength range from 900 to 910 nm , and the reflectance at a wavelength of 1550 nm are shown in Table 3. For example, when the "maximum value of the reflectance in the entire wavelength range" is 20%, it means that "the reflectance in the entire wavelength range is 20% or less".
  • the fired glass-ceramic composition was appropriately pulverized using a mortar to obtain a powder state, and the residual carbon content of the resulting powder was measured using a carbon analyzer (EMIA-320V, manufactured by Horiba, Ltd.). .
  • Table 3 shows the results.
  • the residual carbon content after heat treatment at 900° C. for 12 hours was similarly measured using a carbon analyzer (EMIA-320V manufactured by Horiba, Ltd.).
  • Table 2 shows the results.
  • the glass-ceramic compositions of Examples 1 to 4 had a porosity of 5% or less, and high average strength was obtained.
  • the glass-ceramic composition also had very good reflectance results, which may be attributed to the low residual carbon content.
  • the inorganic pigments used were Pigment F and Pigment A and the compositions were similar, the porosity and residual carbon content in the glass-ceramic compositions were significantly different. . It was suggested that this is because Pigment F was purified by wet pulverization, whereas Pigment A was not purified.
  • the average strength of the glass-ceramic composition of Example 5 was extremely low, resulting in a failure to achieve both low reflectance and suppression of reduction in strength.
  • the inorganic pigments used were Pigment F and Pigment G.
  • Pigment F was subjected to wet pulverization as purification treatment
  • Pigment G was subjected to wet pulverization and high-temperature firing as purification treatment.
  • the average strength of the glass-ceramic composition of Example 7 was extremely low, resulting in a failure to achieve both a low reflectance and suppression of a decrease in strength.

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Abstract

La présente invention concerne une composition de vitrocéramique qui contient une matrice de verre, Al2O3, et un pigment inorganique. La réflectance moyenne à une longueur d'onde de 800 à 880 nm est inférieure ou égale à 30 % ; la réflectance sur toute la plage de longueurs d'onde de 900 à 910 nm est inférieure ou égale à 32 % ; la réflectance à une longueur d'onde de 1 550 nm est inférieure ou égale à 25 % ; la porosité est inférieure ou égale à 10 % ; le pigment inorganique contient un oxyde complexe spécifique ; la teneur en Al2O3 est supérieure à la teneur en matrice de verre ; et la teneur en carbone résiduel dans la composition de vitrocéramique est inférieure ou égale à 20 ppm en masse.
PCT/JP2022/044792 2021-12-10 2022-12-05 Composition de vitrocéramique WO2023106269A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001158641A (ja) * 1999-12-01 2001-06-12 Asahi Glass Co Ltd ガラスおよびガラスセラミックス組成物
WO2011096126A1 (fr) * 2010-02-05 2011-08-11 旭硝子株式会社 Substrat pour le montage d'éléments émetteurs de lumière et dispositif émetteur de lumière
JP2013254820A (ja) * 2012-06-06 2013-12-19 Stanley Electric Co Ltd 発光素子搭載用基板および発光装置
WO2014073604A1 (fr) * 2012-11-07 2014-05-15 旭硝子株式会社 Substrat de céramique vitreuse et boîtier pour équipement électronique portable utilisant ce substrat
JP2017178631A (ja) * 2016-03-28 2017-10-05 日本電気硝子株式会社 真贋認証用ガラスチップの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001158641A (ja) * 1999-12-01 2001-06-12 Asahi Glass Co Ltd ガラスおよびガラスセラミックス組成物
WO2011096126A1 (fr) * 2010-02-05 2011-08-11 旭硝子株式会社 Substrat pour le montage d'éléments émetteurs de lumière et dispositif émetteur de lumière
JP2013254820A (ja) * 2012-06-06 2013-12-19 Stanley Electric Co Ltd 発光素子搭載用基板および発光装置
WO2014073604A1 (fr) * 2012-11-07 2014-05-15 旭硝子株式会社 Substrat de céramique vitreuse et boîtier pour équipement électronique portable utilisant ce substrat
JP2017178631A (ja) * 2016-03-28 2017-10-05 日本電気硝子株式会社 真贋認証用ガラスチップの製造方法

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