JP6963214B2 - Glass powder and sealing material using it - Google Patents
Glass powder and sealing material using it Download PDFInfo
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- JP6963214B2 JP6963214B2 JP2018509132A JP2018509132A JP6963214B2 JP 6963214 B2 JP6963214 B2 JP 6963214B2 JP 2018509132 A JP2018509132 A JP 2018509132A JP 2018509132 A JP2018509132 A JP 2018509132A JP 6963214 B2 JP6963214 B2 JP 6963214B2
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- 239000011521 glass Substances 0.000 title claims description 160
- 239000003566 sealing material Substances 0.000 title claims description 111
- 239000000843 powder Substances 0.000 title claims description 83
- 238000007789 sealing Methods 0.000 claims description 89
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 40
- 239000000945 filler Substances 0.000 claims description 26
- 239000006096 absorbing agent Substances 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- -1 zirconium phosphate compound Chemical class 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052878 cordierite Inorganic materials 0.000 claims description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000174 eucryptite Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 229910052844 willemite Inorganic materials 0.000 claims description 3
- 229910052845 zircon Inorganic materials 0.000 claims description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 71
- 239000000758 substrate Substances 0.000 description 39
- 239000002245 particle Substances 0.000 description 22
- 239000002585 base Substances 0.000 description 19
- 239000003513 alkali Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 12
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 229910002551 Fe-Mn Inorganic materials 0.000 description 9
- 238000004031 devitrification Methods 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 230000031700 light absorption Effects 0.000 description 7
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 6
- 230000001771 impaired effect Effects 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 5
- 230000009970 fire resistant effect Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 4
- 239000002241 glass-ceramic Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- 229910000500 β-quartz Inorganic materials 0.000 description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910019589 Cr—Fe Inorganic materials 0.000 description 1
- 229910017566 Cu-Mn Inorganic materials 0.000 description 1
- 229910017871 Cu—Mn Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910017120 Fe—Mn—Ni Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 238000007572 expansion measurement Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/50—Working by transmitting the laser beam through or within the workpiece
- B23K26/57—Working by transmitting the laser beam through or within the workpiece the laser beam entering a face of the workpiece from which it is transmitted through the workpiece material to work on a different workpiece face, e.g. for effecting removal, fusion splicing, modifying or reforming
-
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
-
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
- C03C3/145—Silica-free oxide glass compositions containing boron containing aluminium or beryllium
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Plasma & Fusion (AREA)
- Mechanical Engineering (AREA)
- Glass Compositions (AREA)
- Laser Beam Processing (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Description
本発明は、ガラス粉末及びそれを用いた封着材料に関し、特にレーザー光による封着処理(以下、レーザー封着)に好適なガラス粉末及びそれを用いた封着材料に関する。 The present invention relates to a glass powder and a sealing material using the same, and particularly to a glass powder suitable for a sealing treatment by laser light (hereinafter, laser sealing) and a sealing material using the same.
近年、フラットディスプレイパネルとして、有機ELディスプレイが注目されている。従来まで、有機ELディスプレイの接着材料として、低温硬化性を有する有機樹脂系接着剤が使用されてきた。しかし、有機樹脂系接着剤では、気体や水分の浸入を完全に遮断できないため、耐水性が低いアクティブ素子や有機発光層が劣化し易く、有機ELディスプレイの表示特性が経時的に劣化するという不具合が生じていた。 In recent years, an organic EL display has been attracting attention as a flat display panel. Conventionally, an organic resin-based adhesive having low-temperature curability has been used as an adhesive material for an organic EL display. However, since the organic resin adhesive cannot completely block the infiltration of gas and moisture, the active element and the organic light emitting layer having low water resistance are liable to deteriorate, and the display characteristics of the organic EL display deteriorate over time. Was occurring.
一方、ガラス粉末を含む封着材料は、有機樹脂系接着剤に比べて、気体や水分が透過し難いため、有機ELディスプレイ内部の気密性を確保することができる。 On the other hand, the sealing material containing the glass powder is less likely to allow gas or moisture to permeate than the organic resin adhesive, so that the airtightness inside the organic EL display can be ensured.
しかし、ガラス粉末は、有機樹脂系接着剤よりも軟化温度が高いため、封着時にアクティブ素子や有機発光層を熱劣化させる虞がある。このような事情から、レーザー封着が着目されている。レーザー封着によれば、封着すべき部分のみを局所的に加熱することが可能であり、アクティブ素子や有機発光層を熱劣化させることなく、無アルカリガラス基板等の被封着物を封着することができる。 However, since the glass powder has a higher softening temperature than the organic resin adhesive, there is a risk that the active element and the organic light emitting layer are thermally deteriorated at the time of sealing. Under these circumstances, laser sealing is drawing attention. According to laser sealing, it is possible to locally heat only the part to be sealed, and the sealed object such as a non-alkali glass substrate can be sealed without thermally deteriorating the active element or the organic light emitting layer. can do.
更に、上記有機ELディスプレイ以外にも、気密パッケージの特性維持や長寿命化を図ることが検討されている。例えば、LED素子が実装された気密パッケージでは、熱伝導性の観点から、基体として、窒化アルミニウム、サーマルビアを有する低温焼成基板(LTCC)が使用されるが、この場合も、基体と蓋(リッド)をレーザー封着することが好ましい。特に、紫外波長領域で発光するLED素子が実装された気密パッケージでは、レーザー封着により紫外波長領域で発光特性を維持し易くなる。更にレーザー封着によりLED素子の熱劣化を防止することもできる。 Further, in addition to the above-mentioned organic EL display, it is being studied to maintain the characteristics of the airtight package and extend the service life. For example, in an airtight package on which an LED element is mounted, a low-temperature firing substrate (LTCC) having aluminum nitride and thermal vias is used as the substrate from the viewpoint of thermal conductivity. In this case as well, the substrate and the lid (lid) are used. ) Is preferably laser-sealed. In particular, in an airtight package in which an LED element that emits light in the ultraviolet wavelength region is mounted, it becomes easy to maintain the emission characteristics in the ultraviolet wavelength region by laser sealing. Further, it is possible to prevent thermal deterioration of the LED element by laser sealing.
本発明者の調査によると、レーザー封着に際し、封着材料の流動性が重要になる。封着材料の流動性が高いと、レーザー封着強度が向上し、機械的衝撃等により気密リーク等が生じ難くなる。そして、封着材料の流動性を向上させるためには、封着材料の低融点化が有効である。 According to the research by the present inventor, the fluidity of the sealing material is important for laser sealing. When the fluidity of the sealing material is high, the laser sealing strength is improved, and airtight leakage or the like is less likely to occur due to mechanical impact or the like. Then, in order to improve the fluidity of the sealing material, it is effective to lower the melting point of the sealing material.
しかし、封着材料の流動性を高めようとすると、耐火性フィラー粉末の含有量を多くしたり、ガラス粉末中に低軟化成分を多くしなければならず、封着材料の熱膨張係数が上昇し易くなる。結果として、無アルカリガラス基板、窒化アルミ基板、LTCC等の被封着物の熱膨張係数に整合し難くなり、被封着物や封着材料層にクラック等が発生し、気密性を確保し難くなる。 However, in order to increase the fluidity of the sealing material, it is necessary to increase the content of the refractory filler powder or increase the softening component in the glass powder, and the coefficient of thermal expansion of the sealing material increases. It becomes easier to do. As a result, it becomes difficult to match the coefficient of thermal expansion of the sealed object such as the non-alkali glass substrate, the aluminum nitride substrate, and the LTCC, cracks occur in the sealed object and the sealing material layer, and it becomes difficult to ensure airtightness. ..
そこで、本発明は、上記事情に鑑みなされたものであり、その技術的課題は、レーザー封着時の流動性が高く、且つ熱膨張係数が低いガラス粉末及びそれを用いた封着材料を創案することにより、有機ELディスプレイ、気密パッケージ等の特性劣化を抑制することである。 Therefore, the present invention has been made in view of the above circumstances, and the technical problem thereof is to devise a glass powder having high fluidity at the time of laser sealing and a low coefficient of thermal expansion and a sealing material using the same. By doing so, it is possible to suppress deterioration of the characteristics of the organic EL display, the airtight package, and the like.
本発明者は、鋭意検討の結果、ガラス粉末のガラス組成範囲を厳密に規制することにより、上記技術的課題を解決し得ることを見出し、本発明として提案するものである。すなわち、本発明のガラス粉末は、ガラス組成として、質量%で、Bi2O3+CuO 83〜95%、Bi2O3 75〜90%、B2O3 3〜12%、ZnO 1〜10%、Al2O3 0〜5%、CuO 4〜15%、Fe2O3 0〜5%、MgO+CaO+SrO+BaO 0〜7%を含有し、実質的にPbOを含有しないことを特徴とする。ここで、「Bi2O3+CuO」は、Bi2O3とCuOの合量を指す。「MgO+CaO+SrO+BaO」は、MgO、CaO、SrO及びBaOの合量を指す。「実質的にPbOを含有しない」とは、ガラス組成中のPbOの含有量が0.1質量%未満の場合を指す。As a result of diligent studies, the present inventor has found that the above technical problems can be solved by strictly regulating the glass composition range of the glass powder, and proposes the present invention. That is, the glass powder of the present invention has a glass composition of Bi 2 O 3 + CuO 83 to 95%, Bi 2 O 3 75 to 90%, B 2 O 3 3 to 12%, ZnO 1 to 10% in terms of glass composition. , Al 2 O 30 to 5%, CuO 4 to 15%, Fe 2 O 30 to 5%, MgO + CaO + SrO + BaO 0 to 7%, and is characterized in that it contains substantially no PbO. Here, "Bi 2 O 3 + CuO" refers to the total amount of Bi 2 O 3 and CuO. "MgO + CaO + SrO + BaO" refers to the total amount of MgO, CaO, SrO and BaO. "Substantially free of PbO" refers to a case where the content of PbO in the glass composition is less than 0.1% by mass.
本発明者の調査によると、Bi2O3とCuOの合量は、レーザー封着時の流動性を高めるために大きな影響を与える。本発明のガラス粉末は、ガラス組成中のBi2O3+CuOの含有量が83〜95質量%である。Bi2O3+CuOの含有量を83質量%以上に規制すると、レーザー封着時の流動性を高めることができる。一方、Bi2O3+CuOの含有量を95質量%以上に規制すると、レーザー封着時にガラスが失透して、所望の流動性を確保し易くなる。According to the investigation by the present inventor, the total amount of Bi 2 O 3 and Cu O has a great influence on increasing the fluidity at the time of laser sealing. The glass powder of the present invention has a Bi 2 O 3 + CuO content of 83 to 95% by mass in the glass composition. If the content of Bi 2 O 3 + CuO is regulated to 83% by mass or more, the fluidity at the time of laser sealing can be improved. On the other hand, if the content of Bi 2 O 3 + CuO is regulated to 95% by mass or more, the glass is devitrified at the time of laser sealing, and it becomes easy to secure the desired fluidity.
また、本発明のガラス粉末は、ガラス組成中のCuOの含有量が4〜15質量%である。CuOの含有量を4質量%以上に規制すると、光吸収特性が向上するため、レーザー封着時の流動性を高めることができる。一方、CuOの含有量を15質量%以下に規制すると、レーザー封着時にガラスが失透し難くなる。 Further, the glass powder of the present invention has a CuO content of 4 to 15% by mass in the glass composition. When the CuO content is regulated to 4% by mass or more, the light absorption characteristics are improved, so that the fluidity at the time of laser sealing can be improved. On the other hand, if the CuO content is restricted to 15% by mass or less, the glass is less likely to be devitrified during laser sealing.
また、本発明のガラス粉末は、ガラス組成中のZnOの含有量が1〜10質量%である。ZnOの含有量を1質量%以上に規制すると、熱膨張係数を低下させることができる。一方、ZnOの含有量を10質量%以下に規制すると、Bi2O3+CuOの含有量が83質量%以上である場合に、レーザー封着時にガラスが失透し難くなる。Further, the glass powder of the present invention has a ZnO content of 1 to 10% by mass in the glass composition. If the ZnO content is regulated to 1% by mass or more, the coefficient of thermal expansion can be reduced. On the other hand, if the ZnO content is restricted to 10% by mass or less, when the Bi 2 O 3 + CuO content is 83% by mass or more, the glass is less likely to be devitrified during laser sealing.
更に、本発明のガラス粉末は、ガラス組成中のMgO+CaO+SrO+BaOの含有量が7質量%以下である。MgO+CaO+SrO+BaOの含有量を7質量%以下に規制すると、レーザー封着時に流動性を確保しながら、熱膨張係数を低下させ易くなる。 Further, the glass powder of the present invention has a content of MgO + CaO + SrO + BaO in the glass composition of 7% by mass or less. If the content of MgO + CaO + SrO + BaO is regulated to 7% by mass or less, the coefficient of thermal expansion tends to be lowered while ensuring the fluidity at the time of laser sealing.
本発明のガラス粉末は、ガラス組成中に実質的にPbOを含有していない。このようにすれば、近年の環境的要請を満たすことができる。 The glass powder of the present invention does not substantially contain PbO in the glass composition. In this way, it is possible to meet the environmental demands of recent years.
第二に、本発明のガラス粉末は、ZnOの含有量が1〜5質量%未満であることが好ましい。 Secondly, the glass powder of the present invention preferably has a ZnO content of less than 1 to 5% by mass.
第三に、本発明のガラス粉末は、質量比(Bi2O3+CuO)/ZnOが15〜70であることが好ましい。ここで、「(Bi2O3+CuO)/ZnO」は、Bi2O3とCuOの合量をZnOの含有量で割った値を指す。Third, the glass powder of the present invention preferably has a mass ratio (Bi 2 O 3 + CuO) / ZnO of 15 to 70. Here, "(Bi 2 O 3 + CuO) / ZnO" refers to a value obtained by dividing the total amount of Bi 2 O 3 and CuO by the content of ZnO.
第四に、本発明のガラス粉末は、MgO+CaO+SrO+BaOの含有量が0〜2.0質量%未満であることが好ましい。このようにすれば、レーザー封着時に良好な流動性を確保しながら、熱膨張係数を確実に低下させることができる。その結果、レーザー封着後の長期信頼性を高めることができる。 Fourth, the glass powder of the present invention preferably has a content of MgO + CaO + SrO + BaO of less than 0 to 2.0% by mass. In this way, the coefficient of thermal expansion can be reliably reduced while ensuring good fluidity during laser sealing. As a result, long-term reliability after laser sealing can be improved.
第五に、本発明の封着材料は、ガラス粉末と耐火性フィラー粉末を含有する封着材料において、ガラス粉末が上記のガラス粉末であり、ガラス粉末の含有量が50〜95体積%であり、耐火性フィラー粉末の含有量が5〜50体積%であることが好ましい。 Fifth, in the sealing material containing the glass powder and the fire-resistant filler powder, the sealing material of the present invention is the above-mentioned glass powder, and the content of the glass powder is 50 to 95% by volume. , The content of the fire resistant filler powder is preferably 5 to 50% by volume.
第六に、本発明の封着材料は、耐火性フィラー粉末が、コーディエライト、ウイレマイト、アルミナ、リン酸ジルコニウム系化合物、ジルコン、ジルコニア、酸化スズ、石英ガラス、β−ユークリプタイト、β−石英固溶体、スポジュメンから選ばれる一種又は二種以上であることが好ましい。これらの耐火性フィラー粉末は、上記ガラス粉末と適合性が良好であり、低熱膨張である。よって、これらの耐火性フィラー粉末を用いると、封着時にガラス粉末を失透させることなく、被封着物の熱膨張係数に整合するように封着材料の熱膨張係数を下げることができる。 Sixth, in the sealing material of the present invention, the refractory filler powder is cordierite, willemite, alumina, zirconium phosphate compound, zircon, zirconia, tin oxide, quartz glass, β-eucryptite, β-. It is preferably one or more selected from quartz solid solution and spojumen. These refractory filler powders have good compatibility with the above glass powders and have low thermal expansion. Therefore, when these refractory filler powders are used, the coefficient of thermal expansion of the sealing material can be lowered so as to match the coefficient of thermal expansion of the object to be sealed without devitrifying the glass powder at the time of sealing.
第七に、本発明の封着材料は、更にレーザー吸収材を0〜25体積%含有することが好ましい。 Seventh, the sealing material of the present invention preferably further contains 0 to 25% by volume of a laser absorber.
第八に、本発明の封着材料は、レーザー吸収材が、Cu系酸化物、Fe系酸化物、Cr系酸化物、Mn系酸化物及びこれらの複合酸化物から選ばれる一種又は二種以上であることが好ましい。このようにすれば、レーザー光を熱エネルギーに変換し易くなるため、レーザー封着強度を高めることができる。ここで、「〜系酸化物」とは、明示の成分を必須成分として含む酸化物を指す。 Eighth, in the sealing material of the present invention, the laser absorber is one or more selected from Cu-based oxides, Fe-based oxides, Cr-based oxides, Mn-based oxides and composite oxides thereof. Is preferable. In this way, the laser light can be easily converted into heat energy, so that the laser sealing strength can be increased. Here, the “~ system oxide” refers to an oxide containing an explicit component as an essential component.
第九に、本発明の封着材料は、レーザー封着に用いることが好ましい。このようにすれば、封着材料層を局所加熱し得るため、耐熱性が低い素子の熱劣化を防止することができる。なお、レーザー封着に使用するレーザー光の光源は、特に限定されないが、例えば半導体レーザー、YAGレーザー、CO2レーザー、エキシマレーザー、赤外レーザー等が、取り扱いが容易な点で好適である。また、レーザー光の発光中心波長は、上記封着材料にレーザー光を的確に吸収させるために、500〜1600nm、特に750〜1300nmが好ましい。Ninth, the sealing material of the present invention is preferably used for laser sealing. By doing so, since the sealing material layer can be locally heated, it is possible to prevent thermal deterioration of the element having low heat resistance. The light source of the laser light 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 suitable because they are easy to handle. Further, the emission center wavelength of the laser light is preferably 500 to 1600 nm, particularly preferably 750 to 1300 nm in order for the sealing material to accurately absorb the laser light.
本発明のガラス粉末は、ガラス組成として、質量%で、Bi2O3+CuO 83〜95%、Bi2O3 75〜90%、B2O3 3〜12%、ZnO 1〜10%、Al2O3 0〜5%、CuO 4〜15%、Fe2O3 0〜5%、MgO+CaO+SrO+BaO 0〜7%を含有し、実質的にPbOを含有しないことを特徴とする。上記のようにガラス粉末のガラス組成範囲を限定した理由を下記に示す。なお、各ガラス成分の説明において、%表示は、質量%を指す。The glass powder of the present invention has a glass composition of Bi 2 O 3 + CuO 83 to 95%, Bi 2 O 3 75 to 90%, B 2 O 3 3 to 12%, ZnO 1 to 10%, Al. It is characterized by containing 2 O 30 to 5%, CuO 4 to 15%, Fe 2 O 30 to 5%, MgO + CaO + SrO + BaO 0 to 7%, and substantially no PbO. The reasons for limiting the glass composition range of the glass powder as described above are shown below. In the description of each glass component,% notation indicates mass%.
Bi2O3とCuOの合量は、レーザー封着時の流動性を高めるために大きな影響を与える。Bi2O3+CuOの含有量は83〜95%であり、好ましくは85〜92%、特に87〜91%である。Bi2O3+CuOの含有量が少な過ぎると、レーザー光を照射しても、ガラスが十分に軟化流動せず、レーザー封着強度を確保し難くなる。但し、Bi2O3+CuOの含有量が多過ぎると、レーザー封着時にガラスが失透して、所望の流動性を確保できなくなる。The total amount of Bi 2 O 3 and Cu O has a great influence on increasing the fluidity at the time of laser sealing. The content of Bi 2 O 3 + CuO is 83 to 95%, preferably 85 to 92%, particularly 87 to 91%. If the content of Bi 2 O 3 + CuO is too small, the glass does not sufficiently soften and flow even when irradiated with laser light, and it becomes difficult to secure the laser sealing strength. However, if the content of Bi 2 O 3 + CuO is too large, the glass will be devitrified during laser sealing, and the desired fluidity cannot be secured.
Bi2O3は、軟化点を下げるための主要成分であり、その含有量は75〜90%であり、好ましくは76〜86%、より好ましくは77超〜84%、更に好ましくは78〜82%である。Bi2O3の含有量が少な過ぎると、軟化点が高くなり過ぎて、レーザー光を照射しても、ガラスが軟化し難くなる。一方、Bi2O3の含有量が多過ぎると、ガラスが熱的に不安定になり、レーザー封着時にガラスが失透し易くなる。Bi 2 O 3 is a main component for lowering the softening point, and its content is 75 to 90%, preferably 76 to 86%, more preferably more than 77 to 84%, still more preferably 78 to 82. %. If the content of Bi 2 O 3 is too small, the softening point becomes too high, and it becomes difficult for the glass to soften even when irradiated with laser light. On the other hand, if the content of Bi 2 O 3 is too large, the glass becomes thermally unstable, and the glass tends to be devitrified at the time of laser sealing.
B2O3は、ガラスネットワークを形成する成分であり、その含有量は3〜12%であり、好ましくは4〜10%、より好ましくは5〜9%である。B2O3の含有量が少な過ぎると、ガラスが熱的に不安定になり、レーザー封着時にガラスが失透し易くなる。一方、B2O3の含有量が多過ぎると、軟化点が高くなり過ぎて、レーザー光を照射しても、ガラスが軟化し難くなる。B 2 O 3 is a component forming a glass network, and its content is 3 to 12%, preferably 4 to 10%, and more preferably 5 to 9%. If the content of B 2 O 3 is too small, the glass becomes thermally unstable, and the glass tends to be devitrified during laser sealing. On the other hand, if the content of B 2 O 3 is too large, the softening point becomes too high, and even if the glass is irradiated with laser light, it becomes difficult for the glass to soften.
ZnOは、熱膨張係数を低下させる成分である。ZnOの含有量は1〜10%であり、好ましくは2〜7%、2.5〜6%、特に3〜5%未満である。ZnOの含有量が少な過ぎると、熱膨張係数が高くなり易い。一方、ZnOの含有量が多過ぎると、Bi2O3+CuOの含有量が83%以上である場合に、ガラスが熱的に不安定になり、レーザー封着時にガラスが失透し易くなる。ZnO is a component that lowers the coefficient of thermal expansion. The ZnO content is 1-10%, preferably 2-7%, 2.5-6%, particularly less than 3-5%. If the ZnO content is too low, the coefficient of thermal expansion tends to be high. On the other hand, if the content of ZnO is too large , the glass becomes thermally unstable when the content of Bi 2 O 3 + CuO is 83% or more, and the glass tends to be devitrified at the time of laser sealing.
質量比(Bi2O3+CuO)/ZnOは、好ましくは15〜70、20〜50、23〜45、特に25〜40である。質量比(Bi2O3+CuO)/ZnOが小さ過ぎると、レーザー光を照射しても、ガラスが十分に軟化流動せず、レーザー封着強度を確保し難くなる。一方、質量比(Bi2O3+CuO)/ZnOが大き過ぎると、熱膨張係数が高くなり易い。The mass ratio (Bi 2 O 3 + CuO) / ZnO is preferably 15 to 70, 20 to 50, 23 to 45, and particularly 25 to 40. If the mass ratio (Bi 2 O 3 + CuO) / ZnO is too small, the glass does not sufficiently soften and flow even when irradiated with laser light, and it becomes difficult to secure the laser sealing strength. On the other hand, if the mass ratio (Bi 2 O 3 + CuO) / ZnO is too large, the coefficient of thermal expansion tends to be high.
Al2O3は、耐水性を高める成分である。その含有量は0〜5%、0〜3%、特に0.1〜2%が好ましい。Al2O3の含有量が多過ぎると、軟化点が高くなり過ぎて、レーザー光を照射しても、ガラスが軟化し難くなる。Al 2 O 3 is a component that enhances water resistance. Its content is preferably 0 to 5%, 0 to 3%, particularly 0.1 to 2%. If the content of Al 2 O 3 is too large, the softening point becomes too high, and even if the glass is irradiated with laser light, it becomes difficult for the glass to soften.
CuOは、光吸収特性を高める成分、つまりレーザー光を吸収して、ガラスを軟化させる成分である。更にBi2O3の含有量が77%より多い場合に、レーザー封着時の失透を抑制する成分である。CuOの含有量は、好ましくは4〜15%、5〜12%、6〜11%、特に7超〜10%である。CuOの含有量が少な過ぎると、光吸収特性が乏しくなり、レーザー光を照射しても、ガラスが軟化し難くなる。一方、CuOの含有量が多過ぎると、ガラス組成中の成分バランスが損なわれて、逆にガラスが失透し易くなる。CuO is a component that enhances the light absorption characteristics, that is, a component that absorbs laser light and softens the glass. Further, when the content of Bi 2 O 3 is more than 77%, it is a component that suppresses devitrification during laser sealing. The content of CuO is preferably 4 to 15%, 5 to 12%, 6 to 11%, particularly more than 7 to 10%. If the content of CuO is too small, the light absorption characteristic becomes poor, and even if the glass is irradiated with laser light, the glass becomes difficult to soften. On the other hand, if the content of CuO is too large, the balance of the components in the glass composition is impaired, and conversely, the glass tends to be devitrified.
Fe2O3は、光吸収特性を高める成分、つまりレーザー光を吸収して、ガラスを軟化させる成分である。更にBi2O3の含有量が77%より多い場合に、レーザー封着時の失透を抑制する成分である。Fe2O3の含有量は、好ましくは0〜5%、0.05〜4%、0.1〜3%、特に0.2〜2%である。Fe2O3の含有量が少な過ぎると、光吸収特性が乏しくなり、レーザー光を照射しても、ガラスが軟化し難くなる。一方、Fe2O3の含有量が多過ぎると、ガラス組成中の成分バランスが損なわれて、逆にガラスが失透し易くなる。Fe 2 O 3 is a component that enhances the light absorption characteristic, that is, a component that absorbs laser light and softens the glass. Further, when the content of Bi 2 O 3 is more than 77%, it is a component that suppresses devitrification during laser sealing. The content of Fe 2 O 3 is preferably 0 to 5%, 0.05 to 4%, 0.1 to 3%, and particularly 0.2 to 2%. If the content of Fe 2 O 3 is too small, the light absorption characteristics are poor, and the glass is difficult to soften even when irradiated with laser light. On the other hand, if the content of Fe 2 O 3 is too large, the component balance in the glass composition is impaired, and conversely, the glass tends to be devitrified.
MgO、CaO、SrO及びBaOは、熱的安定性を高める成分である。しかし、Bi2O3+CuOの含有量が83%以上である場合に、MgO、CaO、SrO及びBaOの合量が多過ぎると、レーザー封着時に流動性を確保しながら、熱膨張係数を低下させることが困難になる。よって、MgO、CaO、SrO及びBaOの合量及び個別含有量は、好ましくは0〜7%、0〜5%、0〜3%、0〜2.0%未満、0〜1%、0〜1.0%未満、0〜0.5%、特に0〜0.1%未満である。MgO, CaO, SrO and BaO are components that enhance thermal stability. However, when the content of Bi 2 O 3 + CuO is 83% or more and the total amount of MgO, CaO, SrO and BaO is too large, the coefficient of thermal expansion is lowered while ensuring fluidity at the time of laser sealing. It becomes difficult to make it. Therefore, the total amount and individual content of MgO, CaO, SrO and BaO are preferably 0 to 7%, 0 to 5%, 0 to 3%, less than 0 to 2.0%, 0 to 1%, 0 to 0. It is less than 1.0%, 0 to 0.5%, especially less than 0 to 0.1%.
質量比(Bi2O3+CuO)/(MgO+CaO+SrO+BaO)は、好ましくは35以上、50以上、100以上、特に150以上である。質量比(Bi2O3+CuO)/(MgO+CaO+SrO+BaO)が小さ過ぎると、レーザー封着時に流動性を確保しながら、熱膨張係数を低下させることが困難になる。なお、「(Bi2O3+CuO)/(MgO+CaO+SrO+BaO)」は、Bi2O3とCuOの合量をMgO、CaO、SrO及びBaOの合量で割った値を指す。The mass ratio (Bi 2 O 3 + CuO) / (MgO + CaO + SrO + BaO) is preferably 35 or more, 50 or more, 100 or more, and particularly 150 or more. If the mass ratio (Bi 2 O 3 + CuO) / (MgO + CaO + SrO + BaO) is too small, it becomes difficult to reduce the coefficient of thermal expansion while ensuring fluidity during laser sealing. In addition, "(Bi 2 O 3 + CuO) / (MgO + CaO + SrO + BaO)" refers to a value obtained by dividing the total amount of Bi 2 O 3 and CuO by the total amount of MgO, CaO, SrO and BaO.
上記の成分以外にも、例えば、以下の成分を導入してもよい。なお、その導入量は、合量で12%以下、10%以下、特に5%以下が好ましい。 In addition to the above components, for example, the following components may be introduced. The total amount to be introduced is preferably 12% or less, 10% or less, and particularly preferably 5% or less.
SiO2は、耐水性を高める成分である。その含有量は0〜10%、0〜5%、特に0〜1%未満が好ましい。SiO2の含有量が多過ぎると、軟化点が高くなり過ぎて、レーザー光を照射しても、ガラスが軟化し難くなる。SiO 2 is a component that enhances water resistance. Its content is preferably 0 to 10%, 0 to 5%, and particularly preferably less than 0 to 1%. If the content of SiO 2 is too large, the softening point becomes too high, and it becomes difficult for the glass to soften even when irradiated with laser light.
Sb2O3は、失透を抑制する成分である。Sb2O3の含有量は、好ましくは0〜5%、0〜2%、特に0〜1%である。Sb2O3は、Bi2O3の含有量が77%より多い場合に、レーザー封着時の失透を抑制する成分である。但し、Sb2O3の含有量が多過ぎると、ガラス組成中の成分バランスが損なわれて、逆にガラスが失透し易くなる。Sb 2 O 3 is a component that suppresses devitrification. The content of Sb 2 O 3 is preferably 0 to 5%, 0 to 2%, and particularly 0 to 1%. Sb 2 O 3 is a component that suppresses devitrification during laser sealing when the content of Bi 2 O 3 is more than 77%. However, if the content of Sb 2 O 3 is too large, the component balance in the glass composition is impaired, and conversely, the glass tends to be devitrified.
Nd2O3は、失透を抑制する成分である。Nd2O3の含有量は、好ましくは0〜5%、0〜2%、特に0〜1%である。Nd2O3は、Bi2O3の含有量が77%より多い場合に、レーザー封着時の失透を抑制する成分である。但し、Nd2O3の含有量が多過ぎると、ガラス組成中の成分バランスが損なわれて、逆にガラスが失透し易くなる。Nd 2 O 3 is a component that suppresses devitrification. The content of Nd 2 O 3 is preferably 0 to 5%, 0 to 2%, and particularly 0 to 1%. Nd 2 O 3 is a component that suppresses devitrification during laser sealing when the content of Bi 2 O 3 is more than 77%. However, if the content of Nd 2 O 3 is too large, the component balance in the glass composition is impaired, and conversely, the glass tends to be devitrified.
Li2O、Na2O、K2O及びCs2Oは、軟化点を低下させる成分であるが、溶融時に失透を助長する作用を有する。よって、これらの成分の含有量は、合量で2%以下、特に1%未満が好ましい。Li 2 O, Na 2 O, K 2 O and Cs 2 O are components that lower the softening point, but have the effect of promoting devitrification during melting. Therefore, the total content of these components is preferably 2% or less, particularly preferably less than 1%.
P2O5は、溶融時の失透を抑制する成分であるが、その添加量が1%より多いと、溶融時にガラスが分相し易くなる。P 2 O 5 is a component that suppresses devitrification during melting, but if the amount added is more than 1%, the glass tends to be phase-separated during melting.
La2O3、Y2O3及びGd2O3は、溶融時の分相を抑制する成分であるが、各々の成分の含有量が3%より多いと、軟化点が高くなり過ぎて、レーザー光を照射しても、ガラスが軟化し難くなる。La 2 O 3 , Y 2 O 3 and Gd 2 O 3 are components that suppress phase separation during melting, but if the content of each component is more than 3%, the softening point becomes too high, and the softening point becomes too high. Even if it is irradiated with laser light, the glass is hard to soften.
NiO、V2O5、CoO、MoO3、TiO2、CeO2及びMnO2は、光吸収特性を高める成分である。各々の成分の含有量は、好ましくは0〜10%、特に0〜7%で未満ある。各々の成分の含有量が多過ぎると、レーザー封着時にガラスが失透し易くなる。NiO, V 2 O 5 , CoO, MoO 3 , TiO 2 , CeO 2 and MnO 2 are components that enhance the light absorption characteristics. The content of each component is preferably less than 0-10%, particularly 0-7%. If the content of each component is too high, the glass tends to be devitrified during laser sealing.
ガラス粉末の最大粒子径Dmaxは、好ましくは10μm以下、特に5μm以下である。ガラス粉末の最大粒子径Dmaxを大き過ぎると、レーザー封着に要する時間が長くなると共に、被封着物間のギャップを均一化し難くなり、レーザー封着の精度が低下し易くなる。ここで、「最大粒子径Dmax」とは、レーザー回折装置で測定した値を指し、レーザー回折法により測定した際の体積基準の累積粒度分布曲線において、その積算量が粒子の小さい方から累積して99%である粒子径を表す。The maximum particle size D max of the glass powder is preferably 10 μm or less, particularly 5 μm or less. If the maximum particle size D max of the glass powder is too large, the time required for laser sealing becomes long, it becomes difficult to make the gap between the objects to be sealed uniform, and the accuracy of laser sealing tends to decrease. Here, the "maximum particle size D max " refers to a value measured by a laser diffractometer, and the cumulative amount is accumulated from the smallest particle in the volume-based cumulative particle size distribution curve measured by the laser diffractometer. The particle size is 99%.
本発明のガラス粉末において、軟化点は、好ましくは480℃以下、450℃以下、特に350〜430℃が好ましい。ガラス粉末の軟化点が高過ぎると、レーザー封着時にガラスが軟化し難くなるため、レーザー光の出力を上昇させない限り、レーザー封着強度を高めることができない。ここで、「軟化点」は、マクロ型示差熱分析で測定した時の第四変曲点の温度を指す。 In the glass powder of the present invention, the softening point is preferably 480 ° C. or lower, 450 ° C. or lower, and particularly preferably 350 to 430 ° C. If the softening point of the glass powder is too high, it becomes difficult for the glass to soften during laser sealing, so that the laser sealing strength cannot be increased unless the output of the laser beam is increased. Here, the "softening point" refers to the temperature of the fourth inflection point as measured by macro-type differential thermal analysis.
本発明の封着材料は、ガラス粉末と耐火性フィラー粉末を含有する封着材料において、ガラス粉末が上記のガラス粉末であり、ガラス粉末の含有量が50〜95体積%であり、耐火性フィラー粉末の含有量が5〜50体積%であることが好ましい。ガラス粉末は、融剤として作用し、レーザー封着時に軟化流動して、被封着物同士を気密一体化させる材料である。耐火性フィラー粉末は、骨材として作用し、封着材料の熱膨張係数を低下させると共に、封着材料層の機械的強度を高める材料である。 The sealing material of the present invention is a sealing material containing a glass powder and a fire-resistant filler powder, wherein the glass powder is the above-mentioned glass powder, the content of the glass powder is 50 to 95% by volume, and the fire-resistant filler is used. The powder content is preferably 5 to 50% by volume. The glass powder is a material that acts as a flux and softens and flows during laser sealing to airtightly integrate the objects to be sealed. The refractory filler powder is a material that acts as an aggregate to reduce the coefficient of thermal expansion of the sealing material and increase the mechanical strength of the sealing material layer.
本発明の封着材料において、耐火性フィラー粉末の含有量は、好ましくは1〜50体積%、10〜45体積%、20〜40体積%、特に22〜35体積%である。耐火性フィラー粉末の含有量が多過ぎると、ガラス粉末の含有量が相対的に少なくなり、所望の流動性、レーザー封着強度を確保し難くなる。なお、耐火性フィラー粉末の含有量が少な過ぎると、耐火性フィラー粉末の添加効果が乏しくなる。 In the sealing material of the present invention, the content of the refractory filler powder is preferably 1 to 50% by volume, 10 to 45% by volume, 20 to 40% by volume, and particularly 22 to 35% by volume. If the content of the refractory filler powder is too large, the content of the glass powder becomes relatively small, and it becomes difficult to secure the desired fluidity and laser sealing strength. If the content of the refractory filler powder is too small, the effect of adding the refractory filler powder becomes poor.
耐火性フィラー粉末として、種々の材料が使用可能であるが、その中でも、コーディエライト、ウイレマイト、アルミナ、リン酸ジルコニウム系化合物、ジルコン、ジルコニア、酸化スズ、石英ガラス、β−ユークリプタイト、β−石英固溶体、スポジュメンが好ましい。これらの耐火性フィラー粉末は、熱膨張係数が低いことに加えて、機械的強度が高く、しかも本発明のガラス粉末との適合性が良好である。 Various materials can be used as the fire-resistant filler powder. Among them, cordierite, willemite, alumina, zirconium phosphate compound, zircon, zirconia, tin oxide, quartz glass, β-eucryptite, β -Quartz solid solution and spojumen are preferable. These refractory filler powders have a low coefficient of thermal expansion, high mechanical strength, and good compatibility with the glass powder of the present invention.
耐火性フィラー粉末の最大粒子径Dmaxは、好ましくは15μm以下、10μm未満、5μm未満、特に0.5〜3μm未満である。耐火性フィラー粉末の最大粒子径Dmaxが大き過ぎると、被封着物間のギャップを均一化し難くなると共に、被封着物間のギャップを狭小化し難くなり、気密パッケージを薄型化、小型化を図り難くなる。なお、被封着物間のギャップが大きい場合に、被封着物と封着材料層の熱膨張係数差が大きいと、被封着物や封着材料層にクラック等が発生し易くなる。The maximum particle size D max of the refractory filler powder is preferably 15 μm or less, less than 10 μm, less than 5 μm, and particularly less than 0.5 to 3 μm. If the maximum particle size D max of the refractory filler powder is too large, it becomes difficult to make the gap between the objects to be sealed uniform, and it becomes difficult to narrow the gap between the objects to be sealed, so that the airtight package can be made thinner and smaller. It becomes difficult. If the gap between the objects to be sealed is large and the difference in the coefficient of thermal expansion between the objects to be sealed and the material layer to be sealed is large, cracks or the like are likely to occur in the objects to be sealed or the material layer to be sealed.
本発明の封着材料は、レーザー光を吸収して熱エネルギーに変換するために、レーザー吸収材を更に含んでいてもよく、その含有量は、好ましくは0〜25体積%、特に0〜10体積%である。レーザー吸収材の含有量が多過ぎると、レーザー封着時に、レーザー吸収材がガラスに溶け込み易くなり、封着材料の熱的安定性が損なわれ易くなる。 The sealing material of the present invention may further contain a laser absorber in order to absorb the laser light and convert it into heat energy, and the content thereof is preferably 0 to 25% by volume, particularly 0 to 10. Volume%. If the content of the laser absorber is too large, the laser absorber tends to melt into the glass during laser sealing, and the thermal stability of the sealing material tends to be impaired.
レーザー吸収材の平均粒子径D50は、好ましくは0.01〜3μm、0.1〜2.5μm、0.3〜2μm、特に0.5〜1.5μmである。また、レーザー吸収材の最大粒子径Dmaxは、好ましくは20μm未満、10μm未満、6μm以下、特に0.5〜4μmである。レーザー吸収材の粒子径が小さ過ぎると、レーザー封着時に、レーザー吸収材がガラスに溶け込み易くなり、封着材料の熱的安定性が損なわれ易くなる。一方、レーザー吸収材の粒子径が大き過ぎると、封着材料中にレーザー吸収材を均一に分散させ難くなり、局所的に封着不良が発生する虞がある。ここで、「平均粒子径D50」とは、レーザー回折装置で測定した値を指し、レーザー回折法により測定した際の体積基準の累積粒度分布曲線において、その積算量が粒子の小さい方から累積して50%である粒子径を表す。The average particle size D 50 of the laser absorber is preferably 0.01 to 3 μm, 0.1 to 2.5 μm, 0.3 to 2 μm, and particularly 0.5 to 1.5 μm. The maximum particle size D max of the laser absorber is preferably less than 20 μm, less than 10 μm, 6 μm or less, and particularly 0.5 to 4 μm. If the particle size of the laser absorber is too small, the laser absorber tends to melt into the glass during laser sealing, and the thermal stability of the sealing material tends to be impaired. On the other hand, if the particle size of the laser absorber is too large, it becomes difficult to uniformly disperse the laser absorber in the sealing material, and there is a possibility that sealing failure may occur locally. Here, "average particle size D 50 " refers to a value measured by a laser diffractometer, and the cumulative amount thereof is cumulative from the smallest particle in the volume-based cumulative particle size distribution curve measured by the laser diffractometer. The particle size is 50%.
レーザー吸収材として、種々の材料が使用可能であるが、その中でも、本発明のガラス粉末との適合性の観点から、Cu系酸化物、Fe系酸化物、Cr系酸化物、Mn系酸化物及びこれらの複合酸化物が好ましい。その中でも、光吸収特性の観点からCu系酸化物及びこの複合酸化物が特に好ましく、本発明のガラス粉末との適合性の観点から、Mn系酸化物及びこの複合酸化物が特に好ましい。 Various materials can be used as the laser absorber, and among them, Cu-based oxides, Fe-based oxides, Cr-based oxides, and Mn-based oxides are used from the viewpoint of compatibility with the glass powder of the present invention. And these composite oxides are preferred. Among them, Cu-based oxides and this composite oxide are particularly preferable from the viewpoint of light absorption characteristics, and Mn-based oxides and this composite oxide are particularly preferable from the viewpoint of compatibility with the glass powder of the present invention.
レーザー吸収材は、黒色であることが好ましい。黒色のレーザー吸収材を用いると、レーザー光の光エネルギーを熱エネルギーに変換し易くなると共に、封着材料中に異物が混入しても、封着材料層に外観不良が生じ難くなる。黒色のレーザー吸収材としては、Al−Cu−Fe−Mn系複合酸化物、Al−Fe−Mn系複合酸化物、Co−Cr−Fe系複合酸化物、Co−Cr−Fe−Mn系複合酸化物、Co−Cr−Fe−Ni系複合酸化物、Co−Cr−Fe−Mn系複合酸化物、Co−Cr−Fe−Ni−Zn系複合酸化物、Co−Fe−Mn−Ni系複合酸化物、Cr−Cu系複合酸化物、Cr−Cu−Mn系複合酸化物、Cr−Fe−Mn系複合酸化物、Fe−Mn系複合酸化物、Cr2O3、Cが好ましく、本発明のガラス粉末との適合性の観点から、Al−Fe−Mn系複合酸化物が特に好ましい。The laser absorber is preferably black. When a black laser absorber is used, it becomes easy to convert the light energy of the laser beam into heat energy, and even if foreign matter is mixed in the sealing material, the appearance of the sealing material layer is less likely to be deteriorated. Examples of the black laser absorber include Al-Cu-Fe-Mn-based composite oxide, Al-Fe-Mn-based composite oxide, Co-Cr-Fe-based composite oxide, and Co-Cr-Fe-Mn-based composite oxidation. Material, Co-Cr-Fe-Ni-based composite oxide, Co-Cr-Fe-Mn-based composite oxide, Co-Cr-Fe-Ni-Zn-based composite oxide, Co-Fe-Mn-Ni-based composite oxidation things, Cr-Cu-based composite oxide, Cr-Cu-Mn-based composite oxide, Cr-Fe-Mn-based composite oxide, Fe-Mn-based composite oxide, Cr 2 O 3, C are preferred, the present invention From the viewpoint of compatibility with glass powder, an Al-Fe-Mn-based composite oxide is particularly preferable.
本発明の封着材料において、熱膨張係数は、好ましくは85×10−7/℃以下、82×10−7/℃以下、79×10−7/℃以下、特に50×10−7/℃以上、且つ76×10−7/℃以下である。このようにすれば、被封着物が低膨張である場合、被封着物や封着材料層に残留する応力が小さくなるため、被封着物や封着材料層にクラックが生じ難くなる。ここで、「熱膨張係数」は、押棒式熱膨張係数測定(TMA)装置で測定した値を指し、測定温度範囲は30〜300℃とする。In the sealing material of the present invention, the coefficient of thermal expansion is preferably 85 × 10 -7 / ° C or less, 82 × 10 -7 / ° C or less, 79 × 10 -7 / ° C or less, and particularly 50 × 10 -7 / ° C. It is above and 76 × 10 -7 / ° C. or less. In this way, when the object to be sealed has a low expansion, the stress remaining on the object to be sealed or the material layer for sealing becomes small, so that cracks are less likely to occur in the material layer to be sealed or the material to be sealed. Here, the "coefficient of thermal expansion" refers to a value measured by a push rod type coefficient of thermal expansion measurement (TMA) device, and the measurement temperature range is 30 to 300 ° C.
本発明の封着材料において、軟化点は、好ましくは510℃以下、480℃以下、特に350〜450℃である。封着材料の軟化点が高過ぎると、レーザー封着時に封着材料層が軟化し難くなるため、レーザー光の出力を上昇させない限り、レーザー封着強度を高めることができない。 In the sealing material of the present invention, the softening point is preferably 510 ° C. or lower, 480 ° C. or lower, and particularly 350 to 450 ° C. If the softening point of the sealing material is too high, the sealing material layer becomes difficult to soften at the time of laser sealing, so that the laser sealing strength cannot be increased unless the output of the laser beam is increased.
本発明の封着材料は、粉末の状態で使用に供してもよいが、ビークルと均一に混練し、封着材料ペーストに加工すると取り扱い易い。ビークルは、主に溶媒と樹脂で構成される。樹脂は、封着材料ペーストの粘性を調整する目的で添加される。また、必要に応じて、界面活性剤、増粘剤等を添加することもできる。封着材料ペーストは、ディスペンサーやスクリーン印刷機等の塗布機を用いて被封着物上に塗布された後、脱バインダー工程に供される。 The sealing material of the present invention may be used in a powder state, 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. Further, if necessary, a surfactant, a thickener and the like can be added. The sealing material paste is applied onto the object to be sealed using a coating machine such as a dispenser or a screen printing machine, and then subjected to a debindering step.
樹脂として、アクリル酸エステル(アクリル樹脂)、エチルセルロース、ポリエチレングリコール誘導体、ニトロセルロース、ポリメチルスチレン、ポリエチレンカーボネート、メタクリル酸エステル等が使用可能である。特に、アクリル酸エステル、ニトロセルロースは、熱分解性が良好であるため、好ましい。 As the resin, acrylic acid ester (acrylic resin), ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, methacrylic acid ester and the like can be used. In particular, acrylic acid ester and nitrocellulose are preferable because they have good thermal decomposability.
溶媒として、N、N’−ジメチルホルムアミド(DMF)、α−ターピネオール、高級アルコール、γ−ブチルラクトン(γ−BL)、テトラリン、ブチルカルビトールアセテート、酢酸エチル、酢酸イソアミル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ベンジルアルコール、トルエン、3−メトキシ−3−メチルブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールジメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノブチルエーテル、プロピレンカーボネート、ジメチルスルホキシド(DMSO)、N−メチル−2−ピロリドン等が使用可能である。 As solvents, N, N'-dimethylformamide (DMF), α-terpineol, higher alcohol, γ-butyl lactone (γ-BL), tetraline, 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.
本発明の封着材料は、レーザー封着時の流動性が高く、且つ熱膨張係数が低いため、気密パッケージのパッケージ基体とガラス蓋のレーザー封着に好適に使用可能である。本発明に係る気密パッケージは、パッケージ基体とガラス蓋とが封着材料層を介して気密封着された気密パッケージにおいて、該封着材料層が、封着材料の焼結体であり、該封着材料が、上記の封着材料であることを特徴とする。以下、本発明に係る気密パッケージについて、詳細に説明する。 Since the sealing material of the present invention has high fluidity at the time of laser sealing and has a low coefficient of thermal expansion, it can be suitably used for laser sealing of a package base of an airtight package and a glass lid. The airtight package according to the present invention is an airtight package in which a package base and a glass lid are airtightly sealed via a sealing material layer, and the sealing material layer is a sintered body of the sealing material, and the sealing is performed. The coating material is the above-mentioned sealing material. Hereinafter, the airtight package according to the present invention will be described in detail.
パッケージ基体は、基部と基部上に設けられた枠部とを有することが好ましい。このようにすれば、パッケージ基体の枠部内にセンサー素子等の内部素子を収容し易くなる。パッケージ基体の枠部は、パッケージ基体の外側端縁領域に沿って、額縁状に形成されていることが好ましい。このようにすれば、デバイスとして機能する有効面積を拡大することができる。またセンサー素子等の内部素子をパッケージ基体内の空間に収容し易くなり、且つ配線接合等も行い易くなる。 The package substrate preferably has a base portion and a frame portion provided on the base portion. By doing so, it becomes easy to accommodate an internal element such as a sensor element in the frame portion of the package substrate. 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 an internal element such as a sensor element in the space inside the package substrate, and it becomes easy to perform wiring joining and the like.
枠部の頂部における封着材料層が配される領域の表面の表面粗さRaは1.0μm未満であることが好ましい。この表面の表面粗さRaが大きくなると、レーザー封着の精度が低下し易くなる。ここで、「表面粗さRa」は、例えば、触針式又は非接触式のレーザー膜厚計や表面粗さ計により測定することができる。 The surface roughness Ra of the surface of the region where the sealing material layer is arranged at the top of the frame portion is preferably less than 1.0 μm. When the surface roughness Ra of this surface becomes large, the accuracy of laser sealing tends to decrease. Here, the "surface roughness Ra" can be measured by, for example, a stylus type or non-contact type laser film thickness meter or a surface roughness meter.
枠部の頂部の幅は、好ましくは100〜7000μm、200〜6000μm、特に300〜5000μmである。枠部の頂部の幅が狭過ぎると、封着材料層と枠部の頂部との位置合わせが困難になる。一方、枠部の頂部の幅が広過ぎると、デバイスとして機能する有効面積が小さくなる。 The width of the top of the frame is preferably 100 to 7000 μm, 200 to 6000 μm, and particularly 300 to 5000 μm. If the width of the top of the frame is too narrow, it becomes difficult to align the sealing material layer with the top of the frame. On the other hand, if the top of the frame is too wide, the effective area that functions as a device becomes small.
パッケージ基体は、ガラスセラミック、窒化アルミニウム、酸化アルミニウムの何れか、或いはこれらの複合材料(例えば、窒化アルミニウムとガラスセラミックを一体化したもの)であることが好ましい。ガラスセラミックは、封着材料層と反応層を形成し易いため、レーザー封着で強固な封着強度を確保することができる。更にサーマルビアを容易に形成し得るため、気密パッケージが過度に温度上昇する事態を適正に防止することができる。窒化アルミニウムと酸化アルミニウムは、放熱性が良好であるため、気密パッケージが過度に温度上昇する事態を適正に防止することができる。 The package substrate is preferably any one of glass ceramic, aluminum nitride, and aluminum oxide, or a composite material thereof (for example, one in which aluminum nitride and glass ceramic are integrated). Since glass-ceramic easily forms a reaction layer with a sealing material layer, a strong sealing strength can be ensured by laser sealing. Further, since the thermal via can be easily formed, the situation where the temperature of the airtight package rises excessively can be appropriately prevented. Since aluminum nitride and aluminum oxide have good heat dissipation, it is possible to appropriately prevent a situation in which the temperature of the airtight package rises excessively.
ガラスセラミック、窒化アルミニウム、酸化アルミニウムは、黒色顔料が分散されている(黒色顔料が分散された状態で焼結されてなる)ことが好ましい。このようにすれば、パッケージ基体が、封着材料層を透過したレーザー光を吸収することができる。その結果レーザー封着の際にパッケージ基体の封着材料層と接触する箇所が加熱されるため、封着材料層とパッケージ基体の界面で反応層の形成を促進することができる。 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). In this way, the package substrate can absorb the laser light transmitted through the sealing material layer. As a result, the portion of the package substrate that comes into contact with the sealing material layer is heated during laser sealing, so that the formation of a reaction layer can be promoted at the interface between the sealing material layer and the package substrate.
黒色顔料が分散されているパッケージ基体は、照射すべきレーザー光を吸収する性質を有すること、例えば、厚み0.5mm、照射すべきレーザー光の波長(808nm)における全光線透過率が10%以下(望ましくは5%以下)であることが好ましい。このようにすれば、パッケージ基体と封着材料層の界面で封着材料層の温度が上がり易くなる。 The package substrate in which the black pigment is dispersed has a property of absorbing the laser light to be irradiated, for example, the total light transmittance at a thickness of 0.5 mm and the wavelength of the laser light to be irradiated (808 nm) is 10% or less. (Preferably 5% or less). In this way, the temperature of the sealing material layer tends to rise at the interface between the package substrate and the sealing material layer.
パッケージ基体の基部の厚みは0.1〜2.5mm、特に0.2〜1.5mmが好ましい。これにより、気密パッケージの薄型化を図ることができる。 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. As a result, the airtight package can be made thinner.
パッケージ基体の枠部の高さ、つまりパッケージ基体から基部の厚みを引いた高さは、好ましくは100〜2500μm、特に200〜1500μmである。このようにすれば、内部素子を適正に収容しつつ、気密パッケージの薄型化を図り易くなる。 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 2500 μm, particularly 200 to 1500 μm. In this way, it becomes easy to reduce the thickness of the airtight package while properly accommodating the internal elements.
ガラス蓋として、種々のガラスが使用可能である。例えば、無アルカリガラス、アルカリホウケイ酸ガラス、ソーダ石灰ガラスが使用可能である。なお、ガラス蓋は、複数枚のガラス板を貼り合わせた積層ガラスであってもよい。 Various glasses can be used as the glass lid. For example, non-alkali glass, alkaline borosilicate glass, and soda-lime glass can be used. The glass lid may be laminated glass in which a plurality of glass plates are bonded together.
ガラス蓋の内部素子側の表面に機能膜を形成してもよく、ガラス蓋の外側の表面に機能膜を形成してもよい。特に機能膜として反射防止膜が好ましい。これにより、ガラス蓋の表面で反射する光を低減することができる。 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. In particular, an antireflection film is preferable as the functional film. As a result, the light reflected on the surface of the glass lid can be reduced.
ガラス蓋の厚みは、好ましくは0.1mm以上、0.15〜2.0mm、特に0.2〜1.0mmである。ガラス蓋の厚みが小さいと、気密パッケージの強度が低下し易くなる。一方、ガラス蓋の厚みが大きいと、気密パッケージの薄型化を図り難くなる。 The thickness of the glass lid is preferably 0.1 mm or more, 0.15 to 2.0 mm, and particularly 0.2 to 1.0 mm. If the thickness of the glass lid is small, the strength of the airtight package tends to decrease. On the other hand, if the glass lid is thick, it becomes difficult to reduce the thickness of the airtight package.
封着材料層は、レーザー光を吸収することにより軟化変形して、パッケージ基体の表層に反応層を形成し、パッケージ基体とガラス蓋とを気密一体化する機能を有している。 The sealing material layer softens and deforms by absorbing laser light to form a reaction layer on the surface layer of the package substrate, and has a function of airtightly integrating the package substrate and the glass lid.
ガラス蓋と封着材料層の熱膨張係数差は50×10−7/℃未満、40×10−7/℃未満、特に30×10−7/℃以下が好ましい。この熱膨張係数差が大き過ぎると、封着部分に残留する応力が不当に高くなり、気密パッケージの気密信頼性が低下し易くなる。The difference in thermal expansion coefficient between the glass lid and the sealing material layer is preferably less than 50 × 10-7 / ° C. and less than 40 × 10-7 / ° C., particularly preferably 30 × 10-7 / ° C. or less. If the difference in the coefficient of thermal expansion is too large, the stress remaining in the sealed portion becomes unreasonably high, and the airtightness reliability of the airtight package tends to decrease.
封着材料層は、枠部との接触位置が枠部の頂部の内側端縁から離間するように形成されると共に、枠部の頂部の外側端縁から離間するように形成することが好ましく、枠部の頂部の内側端縁から50μm以上、60μm以上、70〜2000μm、特に80〜1000μm離間した位置に形成されることが更に好ましい。枠部の頂部の内側端縁と封着材料層の離間距離が短過ぎると、レーザー封着の際に、局所加熱で発生した熱が逃げ難くなるため、冷却過程でガラス蓋が破損し易くなる。一方、枠部の頂部の内側端縁と封着材料層の離間距離が長過ぎると、気密パッケージの小型化が困難になる。また枠部の頂部の外側端縁から50μm以上、60μm以上、70〜2000μm、特に80〜1000μm離間した位置に形成されていることが好ましい。枠部の頂部の外側端縁と封着材料層の離間距離が短過ぎると、レーザー封着の際に、局所加熱で発生した熱が逃げ難くなるため、冷却過程でガラス蓋が破損し易くなる。一方、枠部の頂部の外側端縁と封着材料層の離間距離が長過ぎると、気密パッケージの小型化が困難になる。 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 of the frame and is separated from the outer edge of the top of the frame. It is more preferably formed at a position separated from the inner edge of the top of the frame portion by 50 μm or more, 60 μm or more, 70 to 2000 μm, and particularly 80 to 1000 μm. If the distance between the inner edge of the top of the frame and the sealing material layer is too short, it will be difficult for the heat generated by local heating 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 inner edge of the top of the frame and the sealing material layer is too long, it becomes difficult to miniaturize the airtight package. Further, it is preferably formed at a position separated from the outer edge of the top of the frame portion by 50 μm or more, 60 μm or more, 70 to 2000 μm, and particularly 80 to 1000 μm. 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 during laser sealing is difficult to escape, and the glass lid is 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 becomes difficult to miniaturize the airtight package.
封着材料層は、ガラス蓋との接触位置がガラス蓋の端縁から50μm以上、60μm以上、70〜1500μm、特に80〜800μm離間するように形成されていることが好ましい。ガラス蓋の端縁と封着材料層の離間距離が短過ぎると、レーザー封着の際に、ガラス蓋の端縁領域において、ガラス蓋の内部素子側の表面と外側の表面の表面温度差が大きくなり、ガラス蓋が破損し易くなる。 The sealing material layer is preferably formed so that the contact position with the glass lid is 50 μm or more, 60 μm or more, 70 to 1500 μm, and particularly 80 to 800 μm away from the edge of the glass lid. If the 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 surface of the outer surface of the glass lid in the edge region of the glass lid during laser sealing will increase. It becomes large and the glass lid is easily damaged.
封着材料層は、枠部の頂部の幅方向の中心線上に形成されている、つまり枠部の頂部の中央領域に形成されていることが好ましい。このようにすれば、レーザー封着の際に、局所加熱で発生した熱が逃げ易くなるため、ガラス蓋が破損し難くなる。なお、枠部の頂部の幅が充分に大きい場合は、枠部の頂部の幅方向の中心線上に封着材料層を形成しなくてもよい。 The sealing material layer is preferably formed on the center line in the width direction of the top of the frame, that is, in the central region of the top of the frame. In this way, when the laser is sealed, the heat generated by the local heating can easily escape, so that the glass lid is less likely to be damaged. If the width of the top of the frame is sufficiently large, it is not necessary to form the sealing material layer on the center line in the width direction of the top of the frame.
封着材料層の平均厚みは、好ましくは8.0μm未満、特に1.0μm以上、且つ7.0μm未満である。封着材料層の平均厚みが小さい程、気密パッケージ内のα線放出率が少なくなるため、内部素子のソフトエラーを防止し易くなる。封着材料層の平均厚みが小さい程、レーザー封着の精度が向上する。更に封着材料層とガラス蓋の熱膨張係数が不整合である時に、レーザー封着後に封着部分に残留する応力を低減することもできる。なお、上記のように封着材料層の平均厚みを規制する方法としては、封着材料ペーストを薄く塗布する方法、封着材料層の表面を研磨処理する方法が挙げられる。 The average thickness of the sealing material layer is preferably less than 8.0 μm, particularly 1.0 μm or more and less than 7.0 μm. The smaller the average thickness of the sealing material layer, the smaller the α-ray emission rate in the airtight package, so that it becomes easier to prevent soft errors in the internal element. The smaller the average thickness of the sealing material layer, the better the accuracy of laser sealing. Further, when the coefficient of thermal expansion of the sealing material layer and the glass lid are inconsistent, the stress remaining in the sealing portion after laser sealing can be reduced. Examples of the method for regulating the average thickness of the sealing material layer as described above include a method of applying a thin coating of the sealing material paste and a method of polishing the surface of the sealing material layer.
封着材料層の最大幅は、好ましくは1μm以上、且つ2000μm以下、特に100μm以上、且つ1500μm以下である。封着材料層の最大幅を狭くすると、封着材料層を枠部の端縁から離間させ易くなるため、レーザー封着後に封着部分に残留する応力を低減し易くなる。更にパッケージ基体の枠部の幅を狭くすることができ、デバイスとして機能する有効面積を拡大することができる。一方、封着材料層の最大幅が狭過ぎると、封着材料層に大きなせん断応力がかかると、封着材料層がバルク破壊し易くなる。更にレーザー封着の精度が低下し易くなる。 The maximum width of the sealing material layer is preferably 1 μm or more and 2000 μm or less, particularly 100 μm or more and 1500 μm or less. When the maximum width of the sealing material layer is narrowed, the sealing material layer can be easily separated from the edge of the frame portion, so that the stress remaining in the sealing portion after laser sealing can be easily reduced. Further, the width of the frame portion of the package substrate can be narrowed, and the effective area functioning as a device can be expanded. On the other hand, if the maximum width of the sealing material layer is too narrow, the sealing material layer is likely to be bulk fractured when a large shear stress is applied to the sealing material layer. Further, the accuracy of laser sealing tends to decrease.
以下、図面を参照しながら、本発明を説明する。図1は、本発明に係る気密パッケージの一実施形態を説明するための概略断面図である。図1から分かるように、気密パッケージ1は、パッケージ基体10とガラス蓋11とを備えている。また、パッケージ基体10は、基部12と、基部12の外周端縁上に額縁状の枠部13とを有している。そして、パッケージ基体10の枠部13で囲まれた空間には、内部素子14が収容されている。なお、パッケージ基体10内には、内部素子14と外部を電気的に接続する電気配線(図示されていない)が形成されている。
Hereinafter, the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view for explaining an embodiment of an airtight package according to the present invention. As can be seen from FIG. 1, the airtight package 1 includes a
封着材料層15は、封着材料の焼結体であり、該封着材料は、ガラス粉末と耐火性フィラー粉末を含むが、実質的にレーザー吸収材を含んでいない。そして、このガラス粉末は、ガラス組成として、質量%で、Bi2O3+CuO 83〜95%、Bi2O3 75〜90%、B2O3 3〜12%、ZnO 1〜10%、Al2O3 0〜5%、CuO 4〜15%、Fe2O3 0〜5%、MgO+CaO+SrO+BaO 0〜7%を含有し、実質的にPbOを含有していない。また、封着材料層15は、パッケージ基体10の枠部13の頂部とガラス蓋11の内部素子14側の表面との間に、枠部13の頂部の全周に亘って配されている。封着材料層15の幅は、パッケージ基体10の枠部13の頂部の幅よりも小さく、更にガラス蓋11の端縁から離間している。更に封着材料層15の平均厚みは8.0μm未満になっている。The sealing
上記気密パッケージ1は、次のようにして作製することができる。まず封着材料層15と枠部13の頂部が接するように、封着材料層15が予め形成されたガラス蓋11をパッケージ基体10上に載置する。続いて、押圧治具を用いてガラス蓋11を押圧しながら、ガラス蓋11側から封着材料層15に沿って、レーザー照射装置から出射したレーザー光Lを照射する。これにより、封着材料層15が軟化流動し、パッケージ基体10の枠部13の頂部の表層と反応することで、パッケージ基体10とガラス蓋11が気密一体化されて、気密パッケージ1の気密構造が形成される。
The airtight package 1 can be produced as follows. First, the
実施例に基づいて、本発明を詳細に説明する。なお、以下の実施例は単なる例示である。本発明は、以下の実施例に何ら限定されない。 The present invention will be described in detail based on examples. The following examples are merely examples. The present invention is not limited to the following examples.
表1、2は、本発明の実施例(試料No.1〜11)と比較例(試料No.12〜15)を示している。 Tables 1 and 2 show Examples (Samples Nos. 1 to 11) and Comparative Examples (Samples Nos. 12 to 15) of the present invention.
次のようにして、表中に記載のガラス粉末を作製した。まず表中のガラス組成になるように、各種酸化物、炭酸塩等の原料を調合したガラスバッチを準備し、これを白金坩堝に入れて1000〜1100℃で1〜2時間溶融した。次に、得られた溶融ガラスを水冷ローラーにより薄片状に成形した。最後に、薄片状のガラスをボールミルにて粉砕後、空気分級により、平均粒子径D50が1.0μm、最大粒子径Dmaxが4μmとなるガラス粉末を得た。The glass powders listed in the table were prepared as follows. First, a glass batch containing raw materials such as various oxides and carbonates was prepared so as to have the glass composition shown in the table, and this was placed in a platinum crucible and melted at 1000 to 1100 ° C. for 1 to 2 hours. Next, the obtained molten glass was formed into flakes by a water-cooled roller. Finally, after pulverizing the flaky glass with a ball mill, glass powder having an average particle diameter D 50 of 1.0 μm and a maximum particle diameter D max of 4 μm was obtained by air classification.
耐火物フィラー粉末として、コーディエライト、β−ユークリプタイト及びβ−石英固溶体を用いた。これらの耐火性フィラー粉末は、空気分級により、平均粒子径D501.0μm、最大粒子径Dmax3μmに調整されている。Cordierite, β-eucryptite and β-quartz solid solution were used as the refractory filler powder. These refractory filler powders are adjusted to an average particle size D of 50 1.0 μm and a maximum particle size of D max of 3 μm by air classification.
レーザー吸収材として、Al−Fe−Mn系複合酸化物を用いた。Al−Fe−Mn系複合酸化物の平均粒子径D50は1.0μm、最大粒子径Dmaxは2.5μmであった。An Al—Fe—Mn-based composite oxide was used as the laser absorber. The average particle size D 50 of the Al—Fe—Mn-based composite oxide was 1.0 μm, and the maximum particle size D max was 2.5 μm.
ガラス粉末、耐火性フィラー粉末及びレーザー吸収材を表中に示す混合割合で混合し、試料No.1〜8、12〜14を作製した。またガラス粉末と耐火性フィラー粉末を表中に示す混合割合で混合し、試料No.9〜11、15を作製した。試料No.1〜15につき、熱膨張係数、流動性、レーザー封着強度及び気密性を評価した。 The glass powder, the refractory filler powder, and the laser absorber were mixed at the mixing ratios shown in the table, and the sample No. 1 to 8 and 12 to 14 were prepared. Further, the glass powder and the refractory filler powder were mixed at the mixing ratio shown in the table, and the sample No. 9 to 11 and 15 were prepared. Sample No. The coefficient of thermal expansion, fluidity, laser sealing strength and airtightness were evaluated for 1 to 15.
熱膨張係数は、TMA装置により、30〜300℃の温度範囲で測定した値である。なお、TMAの測定試料として、各試料を緻密に焼結させた後、所定形状に加工したものを用いた。 The coefficient of thermal expansion is a value measured by a TMA device in a temperature range of 30 to 300 ° C. As the TMA measurement sample, each sample was densely sintered and then processed into a predetermined shape.
流動性は、各試料の合成密度に相当する質量の粉末を金型により外径20mmのボタン状に乾式プレスし、これを40mm×40mm×2.8mm厚の高歪点ガラス基板上に載置し、空気中で10℃/分の速度で昇温した後、510℃で10分間保持した上で室温まで10℃/分で降温し、得られたボタンの直径を測定することで評価した。具体的には、流動径が17.5mm以上である場合を「○」、17.5mm未満である場合を「×」として評価した。なお、合成密度とは、ガラス粉末の密度と耐火物フィラー粉末の密度を、表中の体積比で混合させて算出される理論上の密度である。 For fluidity, a powder having a mass corresponding to the synthetic density of each sample is dry-pressed in a button shape with an outer diameter of 20 mm using a mold, and this is placed on a high-strain point glass substrate having a thickness of 40 mm × 40 mm × 2.8 mm. Then, the temperature was raised in air at a rate of 10 ° C./min, the temperature was maintained at 510 ° C. for 10 minutes, the temperature was lowered to room temperature at 10 ° C./min, and the diameter of the obtained button was measured for evaluation. Specifically, the case where the flow diameter was 17.5 mm or more was evaluated as “◯”, and the case where the flow diameter was less than 17.5 mm was evaluated as “x”. The synthetic density is a theoretical density calculated by mixing the density of the glass powder and the density of the refractory filler powder by the volume ratio in the table.
次のようにして、レーザー封着した封着構造体(表中のタイプA)を作製した。まず、各試料とビークル(エチルセルロース樹脂含有のトリプロピレングリコールモノブチルエーテル)を三本ロールミルで均一に混錬し、ペースト化した後、無アルカリガラス基板(日本電気硝子株式会社製OA−10、40mm×0.5mm厚、熱膨張係数38×10−7/℃)上に、無アルカリガラス基板の端縁に沿って額縁状(15μm厚、0.6mm幅)に塗布し、乾燥オーブンで120℃、10分間乾燥した。次に、室温から10℃/分で昇温し、510℃で10分間焼成した後、室温まで10℃/分で降温し、ペースト中の樹脂成分の焼却(脱バインダー処理)及び封着材料の固着を行い、無アルカリガラス基板上に封着材料層を形成した。次に、封着材料層を有する無アルカリガラス基板の上に、封着材料層が形成されていない別の無アルカリガラス基板(40mm×0.5mm厚)を正確に重ねた後、封着材料層を有する無アルカリガラス基板側から、封着材料層に沿って、波長808nmのレーザー光を照射することにより、封着材料層を軟化流動させて、無アルカリガラス基板同士を気密封着した。なお、封着材料層の平均厚みに応じて、レーザー光の照射条件(出力、照射速度)を調整した。最後に、得られた封着構造体を上方1mからコンクリート上に落下させて、レーザー封着した部分に剥離が発生しなかったものを「○」、剥離が発生したものを「×」として、レーザー封着後の接着強度、つまりレーザー封着強度を評価した。A laser-sealed sealing structure (type A in the table) was prepared as follows. First, each sample and vehicle (tripropylene glycol monobutyl ether containing ethyl cellulose resin) are uniformly kneaded with a three-roll mill to form a paste, and then an alkali-free glass substrate (OA-10, 40 mm × manufactured by Nippon Electric Glass Co., Ltd.). On a 0.5 mm thickness, coefficient of thermal expansion of 38 × 10-7 / ° C), apply in a frame shape (15 μm thickness, 0.6 mm width) along the edge of the non-alkali glass substrate, and in a drying oven at 120 ° C. It was dried for 10 minutes. Next, the temperature is raised from room temperature at 10 ° C./min, fired at 510 ° C. for 10 minutes, and then lowered to room temperature at 10 ° C./min to incinerate the resin components in the paste (debinder treatment) and to seal the sealing material. Fixing was performed to form a sealing material layer on a non-alkali glass substrate. Next, another non-alkali glass substrate (40 mm × 0.5 mm thick) on which the sealing material layer is not formed is accurately overlaid on the non-alkali glass substrate having the sealing material layer, and then the sealing material. By irradiating a laser beam having a wavelength of 808 nm from the non-alkali glass substrate side having the layer along the sealing material layer, the sealing material layer was softened and flowed, and the non-alkali glass substrates were air-sealed. The irradiation conditions (output, irradiation speed) of the laser beam were adjusted according to the average thickness of the sealing material layer. Finally, the obtained sealing structure was dropped onto concrete from 1 m above, and the one where peeling did not occur in the laser-sealed part was designated as "○", and the one where peeling occurred was designated as "x". The adhesive strength after laser sealing, that is, the laser sealing strength was evaluated.
更に、次のようにして、レーザー封着した封着構造体(表中のタイプB)を作製した。まず、各試料とビークル(エチルセルロース樹脂含有のトリプロピレングリコールモノブチルエーテル)を三本ロールミルで均一に混錬し、ペースト化した後、アルカリ含有ガラス基板(日本電気硝子株式会社製BDA、10mm×0.2mm厚、熱膨張係数66×10−7/℃)上に、アルカリ含有ガラス基板の端縁に沿って額縁状(15μm厚、0.3mm幅)に塗布し、乾燥オーブンで120℃、10分間乾燥した。次に、室温から10℃/分で昇温し、510℃で10分間焼成した後、室温まで10℃/分で降温し、ペースト中の樹脂成分の焼却(脱バインダー処理)及び封着材料の固着を行い、アルカリ含有ガラス基板上に封着材料層を形成した。次に、封着材料層を有するアルカリ含有ガラス基板の上に、LTCC基板(10mm×1.5mm厚、熱膨張係数66×10−7/℃)を正確に重ねた後、封着材料層を有するアルカリ含有ガラス基板側から、封着材料層に沿って、波長808nmのレーザー光を照射することにより、封着材料層を軟化流動させて、アルカリ含有ガラス基板とLTCC基板を気密封着した。なお、封着材料層の平均厚みに応じて、レーザー光の照射条件(出力、照射速度)を調整した。最後に、得られた封着構造体を上方1mからコンクリート上に落下させて、レーザー封着した部分に剥離が発生しなかったものを「○」、剥離が発生したものを「×」として、レーザー封着後の接着強度、つまりレーザー封着強度を評価した。Further, a laser-sealed sealing structure (type B in the table) was prepared as follows. First, each sample and vehicle (tripropylene glycol monobutyl ether containing ethyl cellulose resin) are uniformly kneaded with a three-roll mill to form a paste, and then an alkali-containing glass substrate (BDA manufactured by Nippon Electric Glass Co., Ltd., 10 mm × 0. 2 mm thick, coefficient of thermal expansion 66 × 10-7 / ° C), applied in a frame shape (15 μm thickness, 0.3 mm width) along the edge of the alkali-containing glass substrate, and placed in a drying oven at 120 ° C. for 10 minutes. It was dry. Next, the temperature is raised from room temperature at 10 ° C./min, fired at 510 ° C. for 10 minutes, and then lowered to room temperature at 10 ° C./min to incinerate the resin components in the paste (debinder treatment) and to seal the sealing material. The fixing was performed to form a sealing material layer on the alkali-containing glass substrate. Next, the LTCC substrate (10 mm × 1.5 mm thickness, coefficient of thermal expansion 66 × 10 -7 / ° C.) is accurately overlaid on the alkali-containing glass substrate having the sealing material layer, and then the sealing material layer is formed. By irradiating the sealing material layer with laser light having a wavelength of 808 nm from the alkali-containing glass substrate side, the sealing material layer was softened and flowed, and the alkali-containing glass substrate and the LTCC substrate were air-sealed. The irradiation conditions (output, irradiation speed) of the laser beam were adjusted according to the average thickness of the sealing material layer. Finally, the obtained sealing structure was dropped onto concrete from 1 m above, and the one where peeling did not occur in the laser-sealed part was designated as "○", and the one where peeling occurred was designated as "x". The adhesive strength after laser sealing, that is, the laser sealing strength was evaluated.
次のようにして、封着構造体(表中のタイプA、B)の気密性を評価した。レーザー封着強度の評価と同様にして、各試料につき封着構造体を作製した。但し、レーザー封着強度の評価とは異なり、レーザー封着前に、封着材料層で形成される額縁の中央部に相当するガラス基板上に、300nm厚の金属Ca膜(タイプA:□25mm、タイプB:□5mm、各)を真空蒸着で形成した。次に、レーザー封着後の封着構造体を121℃、湿度100%、2気圧に保持された恒温恒湿槽内で24時間保持した。その後、金属Ca膜が金属光沢を保持していたものを「○」、透明になったものを「×」として、気密性を評価した。なお、金属Ca膜は、水分と反応すると、透明な水酸化カルシウムになる。 The airtightness of the sealing structure (types A and B in the table) was evaluated as follows. A sealing structure was prepared for each sample in the same manner as in the evaluation of the laser sealing strength. However, unlike the evaluation of laser sealing strength, before laser sealing, a 300 nm thick metal Ca film (type A: □ 25 mm) is placed on a glass substrate corresponding to the central portion of the frame formed by the sealing material layer. , Type B: □ 5 mm, each) was formed by vacuum deposition. Next, the sealed structure after laser sealing was held for 24 hours in a constant temperature and humidity chamber maintained at 121 ° C., 100% humidity, and 2 atm. After that, the airtightness was evaluated by assigning "◯" to the metal Ca film having a metallic luster and "x" to indicate the transparent one. When the metal Ca film reacts with water, it becomes transparent calcium hydroxide.
表1から分かるように、試料No.1〜11は、ガラス粉末のガラス組成が所定範囲に規制されているため、流動性、レーザー封着強度及び気密性の評価が良好であった。一方、試料No.12、15は、ガラス粉末中のCuOを含有しないため、流動性、レーザー封着強度及び気密性の評価が不良であった。試料No.13は、ガラス粉末中のZnOを含有しないため、タイプAの封着構造体においてレーザー封着強度及び気密性の評価が不良であった。試料No.14は、ガラス粉末中のBi2O3+CuOの含有量が少ないため、流動性、レーザー封着強度及び気密性の評価が不良であった。As can be seen from Table 1, the sample No. In Nos. 1 to 11, since the glass composition of the glass powder was regulated within a predetermined range, the evaluation of fluidity, laser sealing strength and airtightness was good. On the other hand, sample No. Since Nos. 12 and 15 did not contain CuO in the glass powder, the evaluation of fluidity, laser sealing strength and airtightness was poor. Sample No. Since No. 13 does not contain ZnO in the glass powder, the evaluation of the laser sealing strength and the airtightness was poor in the type A sealing structure. Sample No. In No. 14, since the content of Bi 2 O 3 + CuO in the glass powder was small, the evaluation of fluidity, laser sealing strength and airtightness was poor.
本発明のガラス粉末及びそれを用いた封着材料は、有機ELディスプレイ、有機EL照明装置等の有機ELデバイスのレーザー封着以外にも、色素増感型太陽電池、CIGS系薄膜化合物太陽電池等の太陽電池のレーザー封着、MEMSパッケージ、LEDパッケージ等の気密パッケージのレーザー封着等にも好適である。 The glass powder of the present invention and the sealing material using the same include dye-sensitized solar cells, CIGS-based thin film compound solar cells, etc., in addition to laser sealing of organic EL devices such as organic EL displays and organic EL lighting devices. It is also suitable for laser sealing of solar cells, OLED packages, laser sealing of airtight packages such as LED packages, and the like.
1 気密パッケージ
10 パッケージ基体
11 ガラス蓋
12 基部
13 枠部
14 内部素子
15 封着材料層
L レーザー光1
Claims (7)
ガラス粉末が請求項1又は2に記載のガラス粉末であり、
ガラス粉末の含有量が50〜95体積%であり、
耐火性フィラー粉末の含有量が5〜50体積%であることを特徴とする封着材料。 In sealing materials containing glass powder, refractory filler powder and laser absorbers
The glass powder is the glass powder according to claim 1 or 2 .
The content of the glass powder is 50 to 95% by volume,
A sealing material characterized in that the content of the refractory filler powder is 5 to 50% by volume.
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