CN112262112B - Sealing material - Google Patents
Sealing material Download PDFInfo
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- CN112262112B CN112262112B CN201980036819.4A CN201980036819A CN112262112B CN 112262112 B CN112262112 B CN 112262112B CN 201980036819 A CN201980036819 A CN 201980036819A CN 112262112 B CN112262112 B CN 112262112B
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- Prior art keywords
- glass
- sealing layer
- refractory filler
- powder
- sealing material
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- 239000003566 sealing material Substances 0.000 title claims abstract description 51
- 239000011521 glass Substances 0.000 claims abstract description 98
- 239000000843 powder Substances 0.000 claims abstract description 96
- 238000007789 sealing Methods 0.000 claims abstract description 77
- 239000000945 filler Substances 0.000 claims abstract description 64
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims description 4
- 230000009970 fire resistant effect Effects 0.000 abstract 3
- 238000010304 firing Methods 0.000 description 14
- 238000005259 measurement Methods 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 239000006066 glass batch Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 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
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- BUUSNVSJZVGMFY-UHFFFAOYSA-N 4-ethylheptane-3,3-diol Chemical compound CCCC(CC)C(O)(O)CC BUUSNVSJZVGMFY-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 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
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 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 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- -1 polyethylene carbonate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010897 surface acoustic wave method Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052844 willemite Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- 229910000500 β-quartz Inorganic materials 0.000 description 1
- 229910052644 β-spodumene Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/02—Containers; Seals
- H01L23/10—Containers; Seals characterised by the material or arrangement of seals between parts, e.g. between cap and base of the container or between leads and walls of the container
-
- H—ELECTRICITY
- H03—ELECTRONIC CIRCUITRY
- H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
- H03H3/00—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators
- H03H3/007—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks
- H03H3/02—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks for the manufacture of piezoelectric or electrostrictive resonators or networks
Abstract
The invention provides a sealing material containing glass powder and refractory filler powder, which is difficult to remain improper stress in a sealing layer and an object to be sealed even if the sealing layer is formed with small thickness. The sealing material is characterized in that (1) the sealing material is used for forming a sealing layer with the thickness of less than 50 mu m, (2) the sealing material contains 50-99% of glass powder and 1-50% of fire-resistant filler powder in volume percent, (3) the fire-resistant filler powder is approximately spherical, (4) the 90% particle diameter D of the fire-resistant filler powder 90 Is 1 to 20 mu m.
Description
Technical Field
The present invention relates to a sealing material for forming a sealing layer having a small thickness, and more particularly to a sealing material suitable for a piezoelectric resonator package or the like having a small size and a small thickness.
Background
In general, a piezoelectric resonator typified by a semiconductor element, a crystal resonator, or a surface acoustic wave element has a plurality of metallized wiring layers made of a high-melting-point metal such as tungsten or molybdenum, and is contained in a package composed of a base body having a recess for containing the piezoelectric resonator at a central portion thereof and made of an alumina insulator, and a lid body composed of an alumina insulator (see, for example, patent document 1).
In the package, one end of the piezoelectric vibrator is fixed to the base by a conductive resin such as a conductive epoxy resin, and each electrode of the piezoelectric vibrator is electrically connected to the metallized wiring layer. In order to hermetically house the piezoelectric resonator in the package, the base and the lid are sealed by a sealing material containing glass powder and refractory filler powder.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2006-261684
Disclosure of Invention
Technical problem to be solved by the invention
In recent years, as portable electronic devices have become popular, there has been an increasing demand for reduction in size and thickness of piezoelectric resonator packages and the like. In order to reduce the size and thickness of a piezoelectric resonator package and the like, it is necessary to reduce the size and thickness of a base body and a lid body, and it is necessary to reduce the thickness of a sealing layer formed of a sealing material.
When a sealing layer having a small thickness is formed on a substrate using a conventional sealing material, a part of the refractory filler powder is exposed on the surface of the sealing layer, and surface protrusions are formed on the sealing layer. When the surface projection is formed on the sealing layer, an improper stress remains in the vicinity of the surface projection of the sealing layer, and an improper stress remains in the lid body abutting against the surface projection, and as a result, a crack is likely to occur in the sealing layer and the lid body by mechanical impact, and the airtightness inside the package body may be impaired.
Further, if a sealing material composed of only glass powder without containing a refractory filler powder is used, it is difficult to cause surface protrusions in the sealing layer. However, since the sealing material made of only glass powder has a high thermal expansion coefficient, it is difficult to match the thermal expansion coefficients of the base body and the lid body, and in this case, an undue stress remains in the base body, the lid body, and the sealing layer, and cracks are likely to occur in the base body, the lid body, and the sealing layer due to mechanical impact, and eventually, the airtightness inside the package may be impaired.
Accordingly, an object of the present invention is to provide a sealing material containing a glass powder and a refractory filler powder, which is less likely to cause an undue stress to remain in a sealing layer or an object to be sealed even when the sealing layer is formed to have a small thickness.
Technical solution for solving technical problem
The inventors of the present invention have conducted extensive studies and found that the above-mentioned problems can be solved by limiting the contents of the glass powder and the refractory filler powder to a predetermined range and limiting the particle size of the refractory filler powder to a predetermined range, and thus the present invention has been proposed. That is, the sealing material of the present invention is characterized in that (1) it is a sealing material for forming a sealing layer having a thickness of 50 μm or less (a sealing thickness of 50 μm or less), (2) the sealing material contains 50 to 99% by volume of a glass powder and 1 to 50% by volume of a refractory filler powder, (3) the refractory filler powder is substantially spherical, and (4) the refractory filler powder has a 90% particle diameter D 90 Is 1 to 20 mu m. The "thickness of the sealing layer" is a thickness after firing, that is, after the sealing step. Wherein "90% particle diameter D 90 "means a value measured by a laser diffraction method, and means a particle diameter (volume) with a cumulative particle diameter of 90%.
The sealing material of the present invention is a sealing material for forming a sealing layer having a thickness of 50 μm or less. If the thickness of the sealing layer is reduced, the piezoelectric vibrator package can be easily reduced in size and thickness. Further, if the thickness of the sealing layer is 50 μm or less, the stress remaining in the sealing layer and the object to be sealed can be relaxed, and the reliability of the piezoelectric resonator package and the like can be improved.
In the sealing material of the present invention, the content of the refractory filler powder is limited to 1 to 50 vol%. This setting enables the coefficient of thermal expansion of the sealing material to be reduced so as to match the coefficient of thermal expansion of the object to be sealed.
In the sealing material of the present invention, the refractory filler powder is limited to a substantially spherical shape. This setting makes it easy to suppress a decrease in the fluidity of the sealing material due to the refractory filler.
In the sealing material of the present invention, the refractory filler powder has a 90% particle diameter D 90 Is limited to 1 to 20 μm. By mixing the refractory filler powder with 90% particle diameter D 90 The restriction to 20 μm or less can reduce the probability of surface protrusion on the sealing layer, and as a result, can prevent the deterioration of the airtightness inside the package due to mechanical impact. In addition, in the case where the coefficient of thermal expansion of the refractory filler powder is low, if the 90% particle diameter D of the refractory filler powder is set 90 If the thickness is 20 μm or less, microcracks are less likely to form on the surface of the sealing layer, and the hermetic sealing inside the package can be further prevented from being impaired by mechanical impact. On the other hand, by mixing the refractory filler powder with 90% particle diameter D 90 The thickness is limited to 1 μm or more, and effects by the refractory filler powder, such as an effect of lowering the thermal expansion coefficient and an effect of improving the mechanical strength of the sealing layer, can be easily obtained.
In the sealing material of the present invention, the glass powder preferably contains TeO in mol% 2 10～60％、MoO 3 10 to 60% and substantially no PbO.
In the sealing material of the present invention, the glass powder preferably contains Ag in mol% 2 O+CuO+WO 3 5 to 50 percent. Wherein, ag 2 O+CuO+WO 3 "means Ag 2 O, cuO and WO 3 The total amount of (a).
The sealing layer of the present invention is characterized in that (1) it is a sealing layer having a thickness of 50 μm or less, (2) the sealing layer contains 50 to 99% by volume of a glass powder and 1 to 50% by volume of a refractory filler powder, (3) the refractory filler powder is substantially spherical, and (4) the refractory filler powder has a 90% particle diameter D 90 1 to 20 μm, and (5) 90% particle diameter D of the refractory filler powder 90 Less than the thickness of the sealing layer.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a sealing material containing a glass powder and a refractory filler powder, which is less likely to cause undue stress to remain in a sealing layer or an object to be sealed even when the sealing layer is formed to have a small thickness.
Drawings
Fig. 1 is a schematic diagram showing a measurement curve obtained by a large-scale differential thermal analysis apparatus.
Detailed Description
First, the sealing material of the present invention will be explained.
The sealing material of the present invention is used for forming a sealing layer having a thickness of 50 μm or less, and the thickness of the sealing layer is preferably 40 μm or less, 30 μm or less, 25 μm or less, 24 μm or less, and particularly 23 μm or less. When the thickness of the sealing layer is too large, it is difficult to reduce the size and thickness of the piezoelectric vibrator package. Further, stress remaining in the sealing layer and the object to be sealed tends to increase, and reliability of the piezoelectric resonator package and the like tends to decrease. The lower limit of the thickness of the sealing layer is not particularly limited, and practically exceeds 1 μm.
In the sealing material of the present invention, the mixing ratio of the glass powder and the refractory filler powder is, in terms of volume%, 50 to 99% of the glass powder, 1 to 50% of the refractory filler powder, preferably 50 to 85% of the glass powder, 15 to 50% of the refractory filler powder, particularly preferably 55 to 75% of the glass powder, and 25 to 45% of the refractory filler powder. When the content of the refractory filler powder is too small, an inappropriate stress tends to remain in the sealing layer and the object to be sealed, and in some cases, cracks may occur in the sealing layer and the object to be sealed, which may cause a poor air-tightness in the piezoelectric resonator package and the like. On the other hand, when the content of the refractory filler powder is too large, the content of the glass powder is relatively small, so that it is difficult to form a dense sealing layer, and the fluidity of the sealing material is liable to be lowered, and as a result, the sealing strength between the members is liable to be lowered.
In the sealing material of the present invention, the thermal expansion coefficient is preferably 20X 10 －7 /℃～180×10 －7 /℃、30×10 －7 /℃～160×10 －7 /. Degree.C, in particular 40X 10 －7 /℃～140×10 －7 V. C. If the coefficient of thermal expansion of the sealing material is too low or too high, there is a possibility that an improper stress remains in the sealing layer and the object to be sealed, and an airtight failure may occur due to mechanical impact, and in some cases, a crack may occur in the sealing layer and the object to be sealed, and an airtight failure may occur in the piezoelectric resonator package and the like. Wherein the "coefficient of thermal expansion" refers to push rod type thermal expansionA value measured by a coefficient of expansion measuring (TMA) device, and a measurement temperature range of 30 to 150 ℃.
In the sealing material of the present invention, the softening point is preferably 400 ℃ or lower, 390 ℃ or lower, 380 ℃ or lower, particularly 370 ℃ or lower. If the softening point is too high, the viscosity of the glass increases, and therefore the sealing temperature increases, which may deteriorate the element during sealing. The lower limit of the softening point is not particularly limited, and is actually 180 ℃ or higher. Wherein "softening point" means the average particle diameter D 50 The glass composition and the sealing material having a thickness of 0.5 to 20 μm are measured as measurement samples by a large differential thermal analyzer. As the measurement conditions, the temperature was measured from room temperature, and the temperature increase rate was set to 10 ℃/min. The softening point measured by a large differential thermal analyzer is the temperature (Ts) at the fourth bending point in the measurement curve shown in fig. 1.
The flexural strength of the sealing material of the present invention is preferably 40MPa or more, 45MPa or more, particularly 50MPa or more. The "flexural strength" is a value obtained by densely sintering a sealing material, processing the sintered sealing material into a prism of 3 × 4 × 40mm as a measurement sample, measuring the value by a three-point load measurement method according to JIS R1601, 20 times each, and calculating an average value thereof. When the bending strength is too low, the sealing layer is easily broken by cracks or the like, and reliability, particularly airtightness of the piezoelectric resonator package or the like is easily deteriorated. The upper limit of the flexural strength is not particularly limited, and is actually 200MPa or less.
Next, the refractory filler used in the present invention will be described.
The refractory filler is substantially spherical. With such a setting, a decrease in the fluidity of the sealing material due to the refractory filler is easily suppressed, and as a result, the sealing strength between the members is easily increased. Further, the closer to a true sphere, the more easily the above-described effects are obtained.
90% particle diameter D of refractory filler powder 90 Is 1 to 20 μm, preferably 1 to 15 μm, 1 to 13 μm, 2 to 12 μm, particularly 3 to 11 μm. 90% particle diameter D of refractory filler powder 90 When too small, not only the effect of lowering the thermal expansion coefficient is deteriorated, but also the refractory filler is used in the heat treatment stepThe frit powder is easily melted into the glass, and thus the fluidity and the devitrification resistance of the sealing material are easily lowered. On the other hand, the 90% particle diameter D of the refractory filler powder 90 If the thickness is too large, surface protrusions tend to be generated in the sealing layer, undue stress tends to remain in the vicinity of the surface protrusions, and cracks tend to be generated in the object to be sealed in contact with the surface protrusions.
90% particle diameter D of refractory filler powder 90 The thickness of the sealing layer is preferably smaller than the thickness of the sealing layer by 5 μm or more, and more preferably smaller than the thickness of the sealing layer by 7 μm or more. 90% particle diameter D of refractory filler powder 90 When the thickness of the sealing layer is not less than the thickness of the sealing layer, surface projections tend to be generated in the sealing layer, an undue stress tends to remain in the vicinity of the surface projections of the sealing layer, and cracks tend to be generated in the object to be sealed which is in contact with the surface projections.
The refractory filler powder is not particularly limited, and various materials can be selected, and a material that is difficult to react with the glass powder is preferable.
Specifically, as the refractory filler, nbZr (PO) may be used 4 ) 3 、Zr 2 WO 4 (PO 4 ) 2 、Zr 2 MoO 4 (PO 4 ) 2 、Hf 2 WO 4 (PO 4 ) 2 、Hf 2 MoO 4 (PO 4 ) 2 Zirconium phosphate, zircon, zirconia, tin oxide, aluminum titanate, quartz, beta-spodumene, mullite, titania, quartz glass, beta-eucryptite, beta-quartz, willemite, cordierite, sr 0.5 Zr 2 (PO 4 ) 3 iso-NaZr 2 (PO 4 ) 3 And 2 or more solid solutions of the type (B) alone or in combination.
Next, the glass powder used in the present invention will be explained.
The glass powder is not particularly limited as long as it has a low softening property. For example, it is preferable that the glass powder contains TeO in mol% 2 10～60％、MoO 3 10 to 60 percent. The reason why the glass composition range is limited as described above will be described below.
TeO 2 Is a component that forms a glass network and improves weatherability. TeO 2 The content of (B) is preferably 10 to 60%, 15 to 57%, particularly 25 to 55%. TeO 2 When the content of (b) is too small, the glass becomes thermally unstable, and the glass is likely to devitrify during melting or firing, and the weather resistance is likely to decrease. TeO, on the other hand 2 When the content (c) is too large, the viscosity (softening point, etc.) of the glass becomes high, low-temperature sealing becomes difficult, and the glass becomes thermally unstable, and the glass is liable to devitrify during melting or firing. Further, the thermal expansion coefficient of the glass tends to be too high.
MoO 3 Is a component that forms a glass network and improves weather resistance. MoO 3 The content of (B) is preferably 10 to 60%, 15 to 55%, particularly 20 to 50%. MoO 3 When the content of (b) is too small, the glass becomes thermally unstable, and the glass is likely to devitrify during melting or firing, and the viscosity (softening point and the like) of the glass becomes high, and low-temperature sealing becomes difficult. On the other hand, moO 3 When the content of (b) is too large, the glass becomes thermally unstable, the glass is easily devitrified during melting or firing, and the thermal expansion coefficient of the glass tends to be too high.
The glass powder may contain the following components in addition to the above components in the glass composition.
Ag 2 O, cuO and WO 3 Is a component that lowers the viscosity (softening point, etc.) of the glass. Ag 2 O+CuO+WO 3 (Ag 2 O, cuO and WO 3 The total amount of (b) is preferably 5 to 50%, 6 to 48%, particularly 7 to 46%. Ag 2 O, cuO and WO 3 When the total amount of (A) is too small, the viscosity (softening point, etc.) of the glass becomes high, and low-temperature sealing tends to be difficult. On the other hand, ag 2 O, cuO and WO 3 When the total amount of (A) is too large, the glass becomes thermally unstable and easily devitrifies during melting or firing.
In addition, ag 2 O, cuO and WO 3 Preferred ranges of the content of (b) are as follows.
Ag 2 The content of O is preferably 0 to 40%, 0 to 35%, particularly 0.1 to 30%.
The content of CuO is preferably 0 to 40%, 0 to 35%, particularly 0.1 to 30%.
WO 3 The content of (b) is preferably 0 to 30%, 0 to 25%, particularly 0 to 20%.
Bi 2 O 3 Is a component that lowers the viscosity (softening point, etc.) of the glass and lowers the thermal expansion coefficient of the glass. Bi 2 O 3 The content of (b) is preferably 0 to 10%, 0 to 6%, particularly 0 to 2%. Bi 2 O 3 When the content of (b) is too large, the glass becomes thermally unstable, and the glass is liable to devitrify during melting or firing.
TiO 2 Is a component that thermally stabilizes glass and lowers the thermal expansion coefficient of glass. TiO 2 2 The content of (B) is preferably 0 to 10%, 0 to 6%, particularly 0 to 2%. TiO 2 2 When the content (c) is too large, the viscosity (softening point, etc.) of the glass becomes high, and low-temperature sealing tends to be difficult.
AgI is a component that lowers the viscosity (softening point, etc.) of the glass. The AgI content is preferably 0 to 10%, 0 to 5%, in particular 0 to 2%. When the content of AgI is too large, the thermal expansion coefficient of the glass tends to be too high.
P 2 O 5 Is a component that forms a glass network and thermally stabilizes the glass. P is 2 O 5 The content of (B) is preferably 0 to 5%, 0 to 2%, particularly 0 to 1%. P 2 O 5 When the content (c) is too large, the viscosity (softening point, etc.) of the glass becomes high, so that low-temperature sealing becomes difficult and weather resistance tends to decrease.
Li 2 O、Na 2 O and K 2 O has an effect of reducing the viscosity (softening point, etc.) of the glass, and the content thereof is preferably 0 to 10%, 0 to 5%, particularly 0 to 2% in total. Li 2 O、Na 2 O and K 2 When the total amount of O is too large, the glass becomes thermally unstable, and the glass is likely to devitrify during melting or firing, and the weather resistance is likely to decrease. In addition, li 2 O、Na 2 O、K 2 The content of O is preferably 0 to 10%, particularly 0 to 5%, respectively.
MgO, caO, srO and BaO have an effect of thermally stabilizing the glass and improving the weather resistance, and the content thereof is preferably 0 to 20%, particularly 0 to 10% in total. When the total amount of MgO, caO, srO and BaO is too large, the glass becomes thermally unstable and is easily devitrified during melting or firing. The contents of MgO, caO, srO, and BaO are preferably 0 to 10%, particularly 0 to 5%, respectively.
ZnO is a component that reduces the viscosity (softening point, etc.) of glass and improves weather resistance. The content of ZnO is preferably 0 to 10%, particularly 0 to 5%. When the content of ZnO is too large, the glass becomes thermally unstable, and the glass is easily devitrified during melting or firing.
Nb 2 O 5 Is a component for thermally stabilizing glass and improving weather resistance. Nb 2 O 5 The content of (b) is preferably 0 to 10%, particularly 0 to 5%. Nb 2 O 5 When the content (c) is too large, the viscosity (softening point, etc.) of the glass becomes high, and low-temperature sealing tends to be difficult.
V 2 O 5 Is a component that forms a glass network and lowers the viscosity (softening point, etc.) of the glass. V 2 O 5 The content of (B) is preferably 0 to 10%, particularly 0 to 5%. V 2 O 5 When the content of (b) is too large, the glass becomes thermally unstable, the glass is easily devitrified during melting or firing, and the weather resistance is easily lowered.
Ga 2 O 3 Is a component for heat-stabilizing glass and improving weather resistance, but is very expensive, and the content thereof is preferably less than 0.01%, and particularly preferably not contained.
SiO 2 、Al 2 O 3 、GeO 2 、Fe 2 O 3 、NiO、CeO 2 、B 2 O 3 、Sb 2 O 3 、ZrO 2 The components are components for thermally stabilizing the glass and inhibiting devitrification, and may be added to less than 2%. When the content is too large, the glass becomes thermally unstable and the glass is liable to devitrify during melting or firing.
For environmental reasons, the glass powder preferably contains substantially no PbO. In the present invention, the phrase "substantially free of PbO" means that the content of PbO in the glass composition is 1000ppm or less.
Next, an example of a method for producing the sealing material of the present invention and a method for using the sealing material of the present invention will be described.
First, the raw material powder prepared to have the above composition is melted at 800 to 1000 ℃ for 1 to 2 hours until homogeneous glass is obtained. Next, the molten glass is formed into a film or the like, and then pulverized and classified to produce glass powder. Further, the average particle diameter D of the glass powder 50 Preferably about 2 to 20 μm.
Next, various refractory filler powders were added to the glass powder to obtain a sealing material.
Next, a vehicle was added to the sealing material and kneaded, thereby preparing a sealing material paste. The vehicle mainly contains an organic solvent and a resin, which is added for the purpose of adjusting the viscosity of the paste. Further, a surfactant, a thickener, or the like may be added as necessary.
The organic solvent is preferably a solvent having a low boiling point (for example, a boiling point of 300 ℃ or less), having a small amount of residue after firing, and not causing glass to change in quality, and the content thereof is preferably 10 to 40% by mass. As the organic solvent, propylene carbonate, toluene, N' -Dimethylformamide (DMF), 1, 3-dimethyl-2-imidazolidinone (DMI), dimethyl carbonate, butyl Carbitol Acetate (BCA), isoamyl acetate, dimethyl sulfoxide, acetone, methyl ethyl ketone, or the like is preferably used. Further, as the organic solvent, higher alcohols are more preferably used. The higher alcohol has viscosity by itself, and thus can be made into a paste without adding a resin to the vehicle. Furthermore, pentanediol and a derivative thereof, specifically diethylpentanediol (C) 9 H 20 O 2 ) Is also excellent in viscosity, and thus can be used for a solvent.
The resin is preferably a resin having a low decomposition temperature, a small amount of residue after firing, and no glass deterioration, and the content thereof is preferably 0.1 to 20% by mass. As the resin, nitrocellulose, polyethylene glycol derivatives, polyethylene carbonate, acrylic esters (acrylic resins), and the like are preferably used.
Next, the paste is applied to a sealed portion between a first member made of metal, ceramic, or glass and a second member made of metal, ceramic, or glass using a dispenser, a screen printer, or the like, dried, and heat-treated at 300 to 400 ℃. By this heat treatment, the sealing material softens and flows, and the first member and the second member are sealed.
The sealing layer formed between the two members in this way is characterized in that the sealing layer has a thickness of 50 μm or less, and contains 50 to 99% by volume of a glass powder and 1 to 50% by volume of a refractory filler powder, the refractory filler powder is substantially spherical, and the refractory filler powder has a 90% particle diameter D 90 1 to 20 mu m, 90% particle diameter D of the refractory filler powder 90 Less than the thickness of the sealing layer.
Examples
The present invention will be described in detail based on examples. Tables 1 to 3 show examples (sample Nos. 1 to 12) and comparative examples (sample Nos. 13 to 15) of the present invention.
[ Table 1]
[ Table 2]
[ Table 3]
First, glass raw materials such as various oxides and carbonates were prepared so as to have glass compositions shown in the table, and after preparing a glass batch, the glass batch was placed in a platinum crucible and melted at 800 to 1000 ℃ for 1 to 2 hours. Next, the film was formed by water cooling. Finally, the filmy glass was pulverized by a ball mill and passed through a sieve having a 75 μm mesh to obtain an average particle diameterD 50 Approximately 10 μm of glass powder.
The refractory filler powder used was the refractory filler powder shown in the table. Each refractory filler powder was prepared in the particle size and shape shown in the table. In addition, ZWP is Zr 2 WO 4 (PO 4 ) 2 NZP is NbZr (PO) 4 ) 3 . The particle diameters of the glass powder and the refractory filler powder were measured by a laser diffraction method.
As shown in the table, the glass powder and the refractory filler powder were mixed to obtain a sealing material. The samples No.1 to 15 were evaluated for thermal expansion coefficient, softening point, flexural strength and fluidity.
The thermal expansion coefficient was determined by a TMA apparatus. The measurement temperature range is set to 30 to 150 ℃.
The softening point was measured using a DTA apparatus. The measurement was carried out at a temperature rising rate of 10 ℃ per minute in the atmosphere, and the measurement was started from room temperature.
The flexural strength was determined by a three-point load cell method in accordance with JIS R1601, wherein each sample was densely sintered and processed into a 3X 4X 40mm prism as a measurement sample. Further, the measurement was performed 20 times each, and the average value was calculated.
The fluidity was evaluated as follows. A powder sample (5 g) was placed in a mold having a diameter of 20mm and press-molded, and then fired at 450 ℃ for 30 minutes on a glass substrate. A sample having a flow diameter of 19mm or more was evaluated as "O", and a sample having a flow diameter of less than 19mm was evaluated as "X".
Next, a sealing layer was produced as follows. First, 963350 mm and an alumina substrate having a thickness of 25mm and 5mm were prepared, and a material obtained by mixing each sample with a vehicle (acrylic resin containing α -terpineol) and pasting the mixture was applied to the entire surface (only one surface) of the substrate. Coating conditions and vehicle composition were prepared so that a sealant layer having a thickness shown in the table could be obtained after the heat treatment. Next, the coated film was dried at 130 ℃ for 10 minutes, the solvent in the vehicle was evaporated, and then heat-treated at 450 ℃ for 30 minutes to obtain the sealing layer shown in the table.
The surface protrusion of the sealing layer obtained by the above method was measured with a surface roughness meter, and a sample having no protrusion of 10 μm or more was evaluated as "o", and a sample having protrusion of 10 μm or more was evaluated as "x".
As can be seen from the table, the samples nos. 1 to 12 as examples of the present invention were able to form the sealing layer having a thickness of 25 μm or less after the heat treatment, and no surface protrusion was observed in the sealing layer.
On the other hand, the sample No.13 as comparative example had poor flowability because the content of the refractory filler powder was too large. The test specimen No.14 was poor in the evaluation of surface projection because the refractory filler powder had a large 90% particle diameter D90. The sample No.15 had poor flowability because the refractory filler powder was crushed.
Industrial applicability
The sealing material of the present invention is suitable for sealing a glass terminal for a semiconductor integrated circuit, a crystal resonator, a flat panel display device, and an LD.
Claims (3)
1. A sealing material characterized by:
(1) Which is a sealing material for forming a sealing layer having a thickness of 50 μm or less,
(2) The sealing material contains 50-99% by volume of glass powder and 1-50% by volume of refractory filler powder, and the glass powder contains MoO in mol% 3 10～60％、Ag 2 O 0～10％、AgI 0～2％、Ag 2 O+CuO+WO 3 5～50％，
(3) The refractory filler powder is substantially spherical in shape,
(4) 90% particle diameter D of refractory filler powder 90 Is 1 to 20 mu m.
2. The seal material of claim 1, wherein:
the glass powder contains TeO in mol% 2 10 to 60%, and substantially does not contain PbO.
3. A sealing layer, characterized by:
(1) Which is a sealing layer having a thickness of 50 μm or less,
(2) The sealing layer contains 50-99% by volume of glass powder and 1-50% by volume of refractory filler powder, and the glass powder contains MoO in mol% 3 10～60％、Ag 2 O 0～10％、AgI 0～2％、Ag 2 O+CuO+WO 3 5～50％，
(3) The refractory filler powder is in the form of a substantially spherical shape,
(4) 90% particle diameter D of refractory filler powder 90 Is 1-20 mu m in diameter,
(5) 90% particle diameter D of refractory filler powder 90 Less than the thickness of the sealing layer.
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| JP2018132784A JP7172209B2 (en) | 2018-07-13 | 2018-07-13 | sealing material |
| JP2018-132784 | 2018-07-13 | ||
| PCT/JP2019/022461 WO2020012833A1 (en) | 2018-07-13 | 2019-06-06 | Sealing material |
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| JP2020011851A (en) | 2020-01-23 |
| WO2020012833A1 (en) | 2020-01-16 |
| CN112262112A (en) | 2021-01-22 |
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