CN106458762B - Ceramic matrix and its manufacturing method - Google Patents
Ceramic matrix and its manufacturing method Download PDFInfo
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- CN106458762B CN106458762B CN201480078508.1A CN201480078508A CN106458762B CN 106458762 B CN106458762 B CN 106458762B CN 201480078508 A CN201480078508 A CN 201480078508A CN 106458762 B CN106458762 B CN 106458762B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 107
- 239000011159 matrix material Substances 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 27
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 27
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 22
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 22
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims description 117
- 238000005452 bending Methods 0.000 claims description 30
- 239000004020 conductor Substances 0.000 claims description 29
- 238000010304 firing Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 239000011656 manganese carbonate Substances 0.000 claims description 14
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 description 34
- 239000000758 substrate Substances 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 22
- 239000002904 solvent Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 13
- 239000011572 manganese Substances 0.000 description 11
- 239000011812 mixed powder Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 230000011218 segmentation Effects 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 239000003566 sealing material Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 229910000679 solder Inorganic materials 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001465 metallisation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000000280 densification Methods 0.000 description 4
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical class CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- 229910001677 galaxite Inorganic materials 0.000 description 4
- 229910052909 inorganic silicate Inorganic materials 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 229910016583 MnAl Inorganic materials 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- WUOACPNHFRMFPN-VIFPVBQESA-N (R)-(+)-alpha-terpineol Chemical compound CC1=CC[C@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-VIFPVBQESA-N 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- 102100035474 DNA polymerase kappa Human genes 0.000 description 2
- 101710108091 DNA polymerase kappa Proteins 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 2
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- -1 phthalic acid ester Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052841 tephroite Inorganic materials 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052834 spessartine Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/111—Fine ceramics
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/111—Fine ceramics
- C04B35/117—Composites
- C04B35/119—Composites with zirconium oxide
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3256—Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6025—Tape casting, e.g. with a doctor blade
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6582—Hydrogen containing atmosphere
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/32—Ceramic
- C04B2237/34—Oxidic
- C04B2237/343—Alumina or aluminates
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0014—Shaping of the substrate, e.g. by moulding
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention relates to a kind of ceramic matrix and its manufacturing methods.Crystalline phase is with Al2O3It only include in addition to this ZrO for main crystalline phase2Crystalline phase.Include: by Al2O3Conversion is calculated as the Al of 89.0~92.0 mass %, by SiO2Conversion is calculated as the Si of 2.0~5.0 mass %, the Mn of 2.0~5.0 mass % is calculated as by MnO conversion, is calculated as the Mg of 0~2.0 mass %, by ZrO by MgO conversion2Conversion is calculated as the Zr of 0.05~2.0 mass %.
Description
Technical field
The present invention relates to a kind of ceramic matrixes, such as are related to being suitable for the ceramic system encapsulation in elements such as internal installation oscillators
The ceramic matrix and its manufacturing method of body, high frequency electric road plate etc..
Background technique
It is ceramic matrix, the i.e. alumina substrate of main crystalline phase as existing ceramic matrix, for example with aluminium oxide, it is known that
No. 4578076 No. 2013/146500 pamphlet of International Publication No., No. 4413223 bulletins of Japanese Patent Publication No., Japanese Patent Publication No. public affairs
The alumina substrate recorded in No. 4220869 report, No. 4413224 bulletins of Japanese Patent Publication No. and Japanese Patent Publication No. bulletins.
In No. 2013/146500 pamphlet of International Publication No., the ceramic packaging body for disclosing a kind of reply miniaturization is used
Matrix contains TiO2(titanium oxide) is used as additive, only contains MnTiO3As crystalline phase than alumina, bending is strong
Degree is 600MPa.
In No. 4413223 bulletins of Japanese Patent Publication No., a kind of ceramic packaging body is disclosed, is to be by 3 bending strengths
What the aluminum oxide sintered body of 500MPa or more was formed, which contains Mn oxide, Si oxide, with Al2O3
It include MnAl for main crystalline phase2O4Crystallize (Mn2SiO4Except).Record comprising Mg oxide, Ca oxide, Sr oxide,
At least one kind of content as other additives in Ba oxide.Also recording can be containing the metal of the transition metal such as W, Mo
The content of powder, oxide powder as coloring components.
In No. 4413224 bulletins of No. 4578076 bulletins of Japanese Patent Publication No. and Japanese Patent Publication No., record by Zr (zirconium),
The alumina substrate that Si (silicon), Mn (manganese), Ti (titanium), Mg (magnesium), Sr (strontium), Ba (barium), Ca (calcium: 2a race) are constituted.The oxidation
Aluminum substrate is that pyroconductivity is 10W/mK or more, and dielectric loss angle tangent is 20 × 10 in 1~60GHz- 4It is below high-strength
The alumina substrate of degree, high heat transfer, low-dielectric loss angle tangent.
In No. 4220869 bulletins of Japanese Patent Publication No., the intensity countermeasure for coping with small-sized packaging body is recorded.It is specific and
Speech, records a kind of manufacturing method of ceramic packaging body, will contain Mn2O3、MgCO3、SiO2Raw cook as additive exists
1350~1500 DEG C are burnt into.
Summary of the invention
The intensity for the ceramic packaging body matrix recorded in No. 2013/146500 pamphlet of International Publication No. is high, still, because
It to be burnt into simultaneously with conductor as Mo (molybdenum), W (tungsten), and is to be burnt under reducing atmosphere, so by Ti4+It is formed
Ti3+During formed hole (hole), cause dielectric loss angle tangent to increase.Installation oscillator etc. packaging body on the way, because
Electric signal loss does not constitute problem caused by the dielectric loss angle tangent of insulator increases, still, in the plate of high frequency electric road
Problem can then be constituted.In addition, because there are MnTiO with high hardness in crystal boundary3Crystalline phase, so dividing chip using compression roller
When, it is easy to happen chipping, in quality, fraction defective (NG rate) is improved.
No. 4413224 bulletins of ceramic packaging body and Japanese Patent Publication No. recorded in No. 4413223 bulletins of Japanese Patent Publication No.
The alumina substrate of middle record is because include MnAl with high hardness2O4Crystalline phase, so with International Publication No. 2013/146500
Pamphlet is same, when using compression roller segmentation chip, is easy to happen chipping, in quality, fraction defective (NG rate) is improved.
The alumina substrate recorded in No. 4413224 bulletins of No. 4578076 bulletins of Japanese Patent Publication No. and Japanese Patent Publication No. with
No. 2013/146500 pamphlet of International Publication No. similarly includes Ti, therefore, because being burnt into simultaneously with Mo conductor, W conductor, institute
Increased with the dielectric loss angle tangent of aluminium oxide ceramics, constitutes problem in the plate of high frequency electric road.
The manufacturing method recorded in No. 4220869 bulletins of Japanese Patent Publication No. by No. 4413223 bulletins of Japanese Patent Publication No. note
It carries content and infers that hypothesis is formed with MnAl2O4Crystalline phase, accordingly, there exist with the skill recorded in No. 4413223 bulletins of Japanese Patent Publication No.
The same problem of art.
The present invention be consider this project and implement, and it is an object of the present invention to provide a kind of ceramic matrix, the ceramic matrix it is curved
Qu Qiangdu high, also, dielectric loss angle tangent is small, is also adapted to high frequency electric road plate, in addition, chipping when chip separation occurs
Rate is also small, can be improved yield rate, can be achieved at low cost the small of the product (ceramic packaging body etc.) for having used ceramic matrix
Type.
In addition, other objects of the present invention are to provide a kind of manufacturing method of ceramic matrix, the manufacture of the ceramic matrix
Method can low fever at a temperature of production bending strength is high, can be realized ceramic packaging body etc. miniaturization ceramic matrix,
It can reduce ceramic matrix and used the cost of the product of ceramic matrix.
[1] feature of ceramic matrix involved in first invention are as follows: its crystalline phase is with Al2O3For main crystalline phase, except this with
It outside, only include ZrO2Crystalline phase.
[2] in such a situation it is preferred to which bending strength is 600MPa or more.
[3] additionally, it is preferred that 1200~1400 DEG C at a temperature of be sintered.
[4] it in first invention, preferably comprises: by Al2O3Conversion is calculated as the Al of 89.0~92.0 mass %, by SiO2It changes
Calculate and is calculated as the Mn of 2.0~5.0 mass % for the Si of 2.0~5.0 mass %, by MnO conversion, is calculated as 0~2.0 by MgO conversion
The Mg of quality %, ZrO is pressed2Conversion is calculated as the Zr of 0.05~2.0 mass %.
The manufacturing method of ceramic matrix involved in [5] second inventions is with Al2O3For the system of the ceramic matrix of main crystalline phase
Make method, which is characterized in that there is the formed body production process of production formed body and by above-mentioned formed body at 1200~1400 DEG C
The firing process being burnt into, the formed body contain the Al of 89.0~92.0 mass %2O3Powder, 2.0~5.0 mass %
SiO2The MnCO of powder, 3.2~8.1 mass % (being calculated as 2.0~5.0 mass % by MnO conversion)3Powder, 0~2.0 mass %
The ZrO of MgO powder, 0.05~2.0 mass %2Powder.
[6] it in the second invention, may further include the process for forming metalliferous conductor layer on formed body, be burnt into
Process is burnt into the formed body for being formed with conductor layer.
[7] in the second invention, firing process can hydrogen content be 5% or more hydrogen and nitrogen forming gas in into
Row.
Related ceramic matrix according to the present invention, bending strength is high, also, dielectric loss angle tangent is small, is also adapted to
High frequency electric road plate can be improved yield rate in addition, chipping incidence when chip separation is also small, can be achieved at low cost
The miniaturization of the product (ceramic packaging body etc.) of ceramic matrix is used.
In addition, the manufacturing method of ceramic matrix involved according to the present invention, can make curved under low firing temperature
The ceramic matrix of the miniaturization of Qu Qiangdu high, achievable ceramic packaging body etc., can reduce ceramic matrix and has used ceramics
The cost of the product of matrix.
Detailed description of the invention
Fig. 1 is the section for indicating the first configuration example (the first packaging body) using ceramic matrix involved in present embodiment
Figure.
Fig. 2 be by the manufacturing method of ceramic matrix involved in present embodiment together with the manufacturing method of the first packaging body
The process block diagram of expression.
Fig. 3 is the section for indicating the second configuration example (the second packaging body) using ceramic matrix involved in present embodiment
Figure.
Fig. 4 be by the manufacturing method of ceramic matrix involved in present embodiment together with the manufacturing method of the second packaging body
The process block diagram of expression.
Fig. 5 A is the top view for indicating polyelectron part substrate, and Fig. 5 B is the amplification of part shown in arrow VB on Fig. 5 A
Figure, Fig. 5 C is the sectional view on the VC-VC line in Fig. 5 B.
Specific embodiment
Hereinafter, referring to Fig.1~Fig. 5 C, to the embodiment example of ceramic matrix according to the present invention and its manufacturing method into
Row explanation.It should be noted that "~" that indicates numberical range in this specification is as the numerical value that will be recorded before and after it as lower limit
Meaning that value and upper limit value include and use.
Ceramic matrix is involved in present embodiment with Al2O3It only include in addition to this ZrO for main crystalline phase2Crystalline phase.
Specifically, it is preferable that comprising: press Al2O3Conversion is calculated as the Al of 89.0~92.0 mass %, by SiO2Conversion is calculated as
The Si of 2.0~5.0 mass %, the Mn that 2.0~5.0 mass % are calculated as by MnO conversion, 0~2.0 mass % is calculated as by MgO conversion
Mg, press ZrO2Conversion is calculated as the Zr of 0.05~2.0 mass %.
Specifically, ceramic matrix is in Al of the production containing 89.0~92.0 mass %2O3Powder, 2.0~5.0 matter
Measure the SiO of %2The MnCO of powder, 3.2~8.1 mass % (being calculated as 2.0~5.0 mass % by MnO conversion)3Powder, 0~2.0 matter
Measure the MgO powder of %, the ZrO of 0.05~2.0 mass %2After the formed body of powder, formed body is carried out at 1200~1400 DEG C
Firing and make.
MgO powder is as Al2O3Sintering aid and add, SiO2Powder is as Al2O3Sintering aid, and
In order to generate Mn2SiO4Glass phase and reduce sintering temperature and add.ZrO2Powder is to inhibit to generate hardness and improve
MnAl2O4And add.
Currently, making that it includes TiO2Powder, Ce2O3Powder, Fe3O4Wantonly a kind or more in powder, still, because dielectric is damaged
It consumes angle tangent to increase, it is advantageous to be free of these substances as far as possible.It is also 0.1 mass % or less even if containing.Dielectric loss angle is just
It cuts in 1MHz~10GHz preferably 30 × 10- 4Below.In turn, preferably 15 × 10- 4Hereinafter, more preferably 10 × 10- 4With
Under.Ceramic matrix can also be applied in the plate of high frequency electric road as a result, be desired.
It should be noted that can according to need makes it contain the 1.0 mass % Mo oxide below as colorant, W oxygen
Compound.
Thereby, it is possible to realize can be sintered in a low temperature of temperature is 1200~1400 DEG C, bending strength is 600MPa or more
Ceramic matrix.
In addition, if Al presses Al2O3Conversion meter is lower than 89.0 mass %, the then Al generated2O3Amount reduce so that bending
Strength reduction.If it exceeds 92.0 mass %, the then Mn generated2SiO4The amount of glass phase is reduced, can not be in 1200~1400 DEG C of realities
It now densifies, further, it enables bending strength reduces.
If Mg by MgO conversion based on more than 2.0 mass %, the Mn generated2SiO4The amount of glass phase is reduced, Wu Fa
1200~1400 DEG C of realization densifications, further, it enables bending strength reduces.
If Si presses SiO2Conversion meter is lower than 2.0 mass %, the then Mn generated2SiO4The amount of glass phase is reduced, Wu Fa
1200~1400 DEG C of realization densifications, further, it enables bending strength reduces.If it exceeds 5.0 mass %, the then Al generated2O3's
Amount is reduced, so that bending strength reduces.
If Mn is lower than 2.0 mass %, the Mn generated based on MnO conversion2SiO4The amount of glass phase is reduced, Wu Fa
1200~1400 DEG C of realization densifications, further, it enables bending strength reduces.If it exceeds 5.0 mass %, the then Al generated2O3's
Amount reduces so that bending strength reduces.In addition, since MnAl can be generated2O4Crystalline phase, thus densify it is impacted so that intensity
It reduces.
If Zr presses ZrO2Conversion meter is lower than 0.05 mass %, then can not inhibit MnAl2O4Generation, such as can not will be sharp
Chipping incidence when dividing chip with compression roller inhibits below 0.1%.If it exceeds 2.0 mass %, then soften, no
The segmentation of chip is easily realized using compression roller.Additionally, there are the tendencies that dielectric loss angle tangent increases.
Therefore, by containing Al, Si, Mn, Mg and Zr by above-mentioned ratio, it can be improved the intensity of the glass phase of generation, tie
Fruit, bending strength improve, and can promote the miniaturization for the product (ceramic packaging body etc.) for having used ceramic matrix.Further, it is possible to
It is made under low firing temperature, is conducive to the cheaper of cost.In turn, pass through the ZrO of generation2Crystalline phase can press down
Hardness processed extremely improves, and can reduce chipping incidence when dividing chip using compression roller, can be improved productivity.
Here, referring to Fig.1~Fig. 4, to 2 of the ceramic packaging body for having used ceramic matrix involved in present embodiment
Configuration example is illustrated.
Ceramic packaging body involved in first configuration example (hereinafter referred to as the first packaging body 10A) has as shown in Figure 1 by this
The multilayer board 12 of the composition of ceramic matrix involved in embodiment and equally the ceramic matrix structure as involved in present embodiment
At lid 14.
Multilayer board 12 be at least by the first substrate 16a of plate, the second substrate 16b of plate and framework 18 in this order
Stacking and constitute.It is formed in the upper surface electrode 20 of the upper surface the second substrate 16b in addition, the multilayer board 12 includes, formed
The lower surface first substrate 16a lower surface electrode 22, be formed in internal internal layer electrode 24, by the internal layer electrode 24 and following table
First through hole 26a, the second through-hole 26b for being electrically connected internal layer electrode 24 and upper surface electrode 20 that face electrode 22 is electrically connected.
In addition, in first packaging body 10A, it is empty in the receiving surrounded by the upper surface of the second substrate 16b and framework 18
Between in 28, quartz crystal unit 30 is electrically connected to upper surface electrode 20 via conductor layer 32.In turn, it in order to protect quartz crystal unit 30, covers
Body 14 is hermetically sealed via glassy layer 34 in the upper surface of framework 18.
In above-mentioned first packaging body 10A, the example for being mounted with quartz crystal unit 30 in accommodating space 28 is given, removes this
In addition, resistor, filter, capacitor, at least one or more in semiconductor element can also be installed.In the present embodiment,
Dielectric loss angle tangent is 30 × 10 in 1MHz~10GHz- 4Hereinafter, therefore, also being suitable as high frequency electric road plate.
Also, because the multilayer board 12 and lid 14 of the first packaging body 10A of composition are made pottery as involved in present embodiment
Porcelain basal body is constituted, so bending strength is 600MPa or more.If bending strength is lower than 600MPa, may be sealed in lid 14
When and when 2 installations apply thermal stress and destroy.Or, it is possible to when operation and the impact etc. of the when of use due tos, destroy.
As long as bending strength is in 600MPa or more, it will be able to avoid such destruction risk.In addition, even if not carrying out table to ceramic matrix
The multilayer board 12 and lid 14 for functioning as the first packaging body 10A are ground in face, can also prevent from carrying out hermetic lid 14
It is destroyed when sealing, the manufacturing cost and reliability of the first packaging body 10A can be improved.It should be noted that " bending strength " is
Refer to 4 bending strengths, is the value measured at room temperature based on JISR1601 (bend test method of fine ceramics).
In addition, can be 1200 in temperature because ceramic matrix involved in present embodiment has above-mentioned composition
Make its sintering in a low temperature of~1400 DEG C.Therefore, by by the presoma (formed body before firing) of ceramic matrix, electrode (on
Surface electrode 20, lower surface electrode 22, internal layer electrode 24) and through-hole 26 (first through hole 26a, the second through-hole 26b) be burnt into simultaneously,
Multilayer board 12 can be made, manufacturing process can be simplified.
Next, according to the manufacturing method of such as the first packaging body 10A, referring to Fig. 2, to the manufacturing method of ceramic matrix into
Row explanation.
Firstly, preparing the Al containing 89.0~92.0 mass % in the step S1a of Fig. 22O3Powder, 2.0~5.0 matter
Measure the SiO of %2The MnCO of powder, 3.2~8.1 mass %3Powder, the MgO powder of 0~2.0 mass %, 0.05~2.0 mass %
ZrO2The mixed-powder of powder prepares organic principle (bonding agent) in step S1b, in step S1c, prepares solvent.
Al2O3The average grain diameter of powder is preferably 0.7~2.5 μm.If being lower than 0.7 μm, because generating MnAl2O4Knot
Crystal phase, so densification is impacted, so that strength reduction.If it exceeds 2.5 μm, then Al2O3The agglutinating property of itself reduces, so that
Strength reduction.
SiO2The average grain diameter of powder is preferably 0.1~2.5 μm.MnCO3The average grain diameter of powder is preferably 0.5~4.0 μ
m.The average grain diameter of MgO powder is preferably 0.1~1.0 μm.ZrO2The average grain diameter of powder is preferably 0.3~1.0 μm.
For these SiO2Powder, MnCO3Powder, MgO powder, ZrO2For powder, if being lower than the lower limit of preferred scope
Value, then particles aggregate, dispersibility reduce, and cause composition not to be homogenized, strength reduction.If it exceeds the upper limit of preferred scope
Value, then lead to becoming large-sized for particle itself, so being difficult to disperse uniform particle, causes composition not to be homogenized, strength reduction.
The organic principle (bonding agent) prepared in step S1b can enumerate resin, surfactant, plasticizer etc..Make
For resin, it can be cited for example that polyvinyl butyral, as surfactant, it can be cited for example that tertiary amine, as plasticizer,
It can be cited for example that phthalic acid ester (such as phthalic acid diisononyl esters: DINP).
The solvent prepared in step S1c can enumerate alcohol series solvent, aromatic system solvent etc..It, can as alcohol series solvent
To enumerate such as IPA (isopropanol), as aromatic system solvent, it can be cited for example that toluene.
Then, in following step S2, after so that organic principle and solvent are mixed, are dispersed in above-mentioned mixed-powder,
In step s3, by the production of forming method well known to extrusion, scraper method, rolling process, injection method etc. as before ceramic matrix
Drive the ceramic mouldings (also referred to as ceramic band) of body.Such as organic principle, solvent are added in mixed-powder, it is modulated into slurry
Afterwards, the ceramic band of specific thickness is formed by scraper method.Alternatively, organic principle is added in mixed-powder, by extrusion forming,
Calendering formation etc. and the ceramic band for making specific thickness.
In step s 4, ceramic band is cut into desired shape, is processed, make the large area of first substrate
First band, the second band of the large area of the second substrate, the 4th band of the third band of framework and lid pass through in turn
The formation such as microbit processing, laser processing are used to form the through hole of first through hole 26a and the second through-hole 26b.
Next, in step s 5, by the methods of silk-screen printing, intaglio printing, to made as described above
One band and the second band printing are coated with and are used to form the conductor paste of upper surface electrode 20, lower surface electrode 22, internal layer electrode 24, into
And as needed, conductor paste is filled into through hole.
Conductor paste preferably as conductor ingredient using in the refractory metal such as W (tungsten), Mo (molybdenum) it is at least one kind of,
Al is wherein added to such as 1~20 mass %, particularly 8 mass % ratios below2O3Powder or SiO2Powder or with pottery
The conductor paste of the identical powder of porcelain basal body.Thereby, it is possible to maintain low-level by the conducting resistance of conductor layer while improving
The adhesion of alumina sintered body and conductor layer can prevent a problem that electroplated layer lacks.
Then, in step s 6, printing is coated with to the first band of conductor paste and the third band of the second band and framework
Contraposition carries out stacking crimping, makes laminated body.
Then, in the step s 7, cut for example, by knife and form the segmentation groove for dividing chip on the two sides of laminated body.
In following step S8, by the molding gas of hydrogen and nitrogen that laminated body and the 4th band are 5% or more in hydrogen content
Body atmosphere, such as H2/N2With 1200~1400 DEG C in=30%/70% forming gas atmosphere (25~47 DEG C of fogger temperature)
Temperature range be burnt into.Stacking raw sheet (the polyelectron component base that laminated body and conductor paste are burnt into simultaneously is made as a result,
Plate).By the firing, crystalline phase as described above can be made with Al2O3It only include in addition to this ZrO for main crystalline phase2Crystallization
The ceramic matrix of phase, i.e. polyelectron part substrate.
Because the atmosphere being burnt into is forming gas atmosphere as described above, thus, it is possible to prevent the metal in conductor paste
Oxidation.The preferably above-mentioned temperature range of firing temperature.If firing temperature is lower than 1200 DEG C, densify insufficient, bending is strong
600MPa is not achieved in degree, in addition, constituting the contraction of the first band, the second band and third band of laminated body if being higher than 1400 DEG C
The unevenness of rate becomes larger, and dimensional accuracy reduces.This will lead to yield rate reduction, so that cost high price.Certainly, as long as firing temperature
Degree increases, and will there are problems that equipment cost correspondingly increases.
Next, in step s 9, carrying out electroplating processes to above-mentioned polyelectron part substrate, being formed in the polyelectron portion
The conductor layer of part substrate surface is formed by least one kind of electroplated layer constituted in Ni, Co, Cr, Au, Pd and Cu, in polyelectron portion
Part substrate surface forms multiple upper surface electrodes 20 and multiple lower surface electrodes 22.
Then, in step slo, it is pushed against with compression roller etc. and polyelectron part substrate is divided into multiple (chip separations),
Make multiple multilayer boards 12 with accommodating space 28.In step s 11, in each accommodating space 28 of multiple multilayer boards 12
It is interior, quartz crystal unit 30 is installed on upper surface electrode 20 via conductor layer 32 respectively.
Then, in step s 12, in the upper surface of each multilayer board 12, with the ceramics for being formed with glass for sealing layer 34
Lid 14 processed is hermetic sealed, to complete to be equipped with multiple first packaging body 10A of quartz crystal unit 30 in inside.
In the manufacturing method (manufacturing method of ceramic matrix) of first packaging body 10A, knot as described above can be made
Crystal phase is with Al2O3It only include in addition to this ZrO for main crystalline phase2Crystalline phase, bending strength are the ceramic base of 600MPa or more
Body.That is, the miniaturization that ceramic packaging body etc. can be achieved and slimming and bending strength can be made under low firing temperature
The ceramic matrix being improved can reduce ceramic matrix and use the cost of the product of ceramic matrix.
Next, referring to Fig. 3 and Fig. 4, to (hereinafter referred to as the second packaging body of ceramic packaging body involved in the second configuration example
10B) it is illustrated.
Second packaging body 10B has as shown in Figure 3 almost similarly to be constituted with above-mentioned first packaging body 10A, but with
Lower aspect is different.
That is, metal cap body 40 to be hermetically sealed in the frame of multilayer board 12 using the high-temperature sealing materials such as silver solder 42
On body 18.
In addition, between the upper surface and high-temperature sealing material 42 of the framework 18 of multilayer board 12, there are bonding layers 44.It should
Bonding layer 44 the upper surface of framework 18 have formed by material identical with upper surface electrode 20 metalization layer 46, be formed in
For example golden (Au) nothing that such as nickel (Ni) in the metalization layer 46 is electrolysed electroplated layer 48, is formed on Ni electrolysis electroplated layer 48
It is electrolysed electroplated layer 50.
Metal cap body 40 is formed as the tabular of 0.05~0.20mm of thickness, by Fe-Ni alloy plate or iron-nickel-cobalt
Alloy sheets are constituted.In the lower surface (whole face or part) corresponding to framework 18 of the metal cap body 40, it is formed with as high temperature
The solders such as the silver-copper eutectic solder of sealing material 42.With a thickness of 5~20 μm or so.
Specifically, metal cap body 40 is that following composite plate is punched into regulation shape with blanking die and is made, this is multiple
Plywood is the solder foils such as silver-copper solder to be overlapped to Fe-Ni alloy plate or the lower surface of iron-nickel-cobalt alloy sheets is gone forward side by side
Row calendering and constitute.
As high-temperature sealing material 42, specifically, solder 1 (85Ag-15Cu) shown in following table 1, weldering can be used
Expect any one of 2 (72Ag-28Cu), solder 3 (67Ag-29Cu-4Sn).
[table 1]
Ni is electrolysed electroplated layer 48 and Au electroless plating layer 50 as raising high-temperature sealing material 42 to metalization layer 46
The layer of wetability plays a role.
Next, being illustrated referring to Fig. 4 to the manufacturing method of the second packaging body 10B.It should be noted that for Fig. 2 weight
Multiple process, omits the description.
Firstly, preparing the mixed-powder, organic principle and solvent for making ceramic band in the step S101 of Fig. 4.It is quasi-
Standby mixed-powder, organic principle and solvent is identical as above-mentioned steps S1a, step S1b and step S1c, so omitting its repetition
Explanation.
Then, in step s 102, after so that organic principle and solvent are mixed, are dispersed in above-mentioned mixed-powder, in step
In S103, ceramic matrix presoma is used as by the production of forming method well known to extrusion, scraper method, rolling process, injection method etc.
Ceramic mouldings (ceramic band).
In step S104, ceramic band is cut off to and is processed into desired shape, makes the big face of first substrate 16a
The third band of second band of the large area of long-pending first band, the second substrate 16b, framework 18, in turn, by microbit plus
The formation such as work, laser processing are used to form the through hole of first through hole 26a and the second through-hole 26b.
On the other hand, in step s105, prepare raw material powder, organic principle and the solvent of conductor paste.The original of preparation
Feed powder end can enumerate at least one kind of in the metal powders such as W (tungsten), Mo (molybdenum), nickel (Ni) and as described above wherein with such as 1
~20 mass %, particularly 8 mass % ratios below are properly added Al2O3Powder or SiO2Powder or with ceramic matrix phase
Mixed-powder obtained by same powder.The organic principle of preparation can enumerate resin (such as ethyl cellulose), surfactant
Deng.The solvent of preparation can enumerate terpenol (terpenol) etc..
Then, in step s 106, so that organic principle and solvent are mixed, are dispersed in above-mentioned mixed-powder, modulate conductor
Paste.
Next, in step s 107, by the methods of silk-screen printing, intaglio printing to made as described above
One band~third band printing coating conductor paste.
Then, in step S108, first band~third band that printing is coated with conductor paste is aligned, stacking crimping, system
Make laminated body.
Then, it in step S109, is cut for example, by knife and forms the segmentation ditch for dividing chip on the two sides of laminated body
Slot.
In following step S110, by laminated body in H2/N2=30%/70% forming gas atmosphere (fogger temperature
Degree 25~47 DEG C) in be burnt into 1200~1400 DEG C of temperature range.It makes laminated body as a result, and conductor paste is burnt simultaneously
At stacking raw sheet (polyelectron part substrate).There are the polyelectron part substrate multiple frameworks 18 to be aligned to integrated shape
Shape.In addition, conductor paste becomes electrode (upper surface electrode 20 etc.), metalization layer 46 by the firing.
In following step S111, the surface (pre-treatment) of metalization layer 46 is at least cleaned with alkali, acid etc..That is,
After carrying out alkali cleaning, sour cleaning is carried out.In preceding processing, alkali and acid can be diluted to concentration appropriate carry out using.In addition, preceding
The temperature handled at 20 DEG C~70 DEG C or so implements a few minutes~dozens of minutes.
In step S112, electroplating processes are electrolysed by carrying out Ni, Ni is formed in metalization layer 46 and is electrolysed electroplated layer 48
(film thickness: 1.0~5.0 μm).
In step S113, after carrying out the processing of palladium (Pd) electroless plating, the processing of Au electroless plating is carried out, is electrolysed in Ni
Au electroless plating layer 50 (film thickness: 0.05~0.3 μm) is formed on electroplated layer 48.
Then, it in step S114, is pushed against with compression roller etc. and polyelectron part substrate is divided into multiple (chip separations),
Production has multiple multilayer boards 12 of accommodating space 28 respectively.Then, in step sl 15, in each of multiple multilayer boards 12
In accommodating space 28, quartz crystal unit 30 is installed on upper surface electrode 20 via conductor layer 32 respectively.
Then, in step S116, keep upper surface (bonding layer 44) side of high-temperature sealing material 42 and framework 18 opposed and
The metal cap body 40 for making the back side form high-temperature sealing material 42 is covered in framework 18.Then, make a pair of rolls electricity of seam welder
Pole is contacted on one side in the opposite outer peripheral edge of metal cap body 40, is rotated on one side, and by flowing through electric current between the roller electrode,
Metal cap body 40, is thus hermetically sealed in framework 18 by a part melting for making high-temperature sealing material 42.When sealing
Atmosphere is in N2It is carried out in gas or vacuum.It completes that multiple second packaging bodies of quartz crystal unit 30 are installed in inside as a result,
10B。
Embodiment
For Examples 1 to 4, comparative example 1~7, it is thus identified that ceramic matrix removes Al2O3Crystalline phase, bending strength in addition
(flexural strength), dielectric loss angle tangent, chipping incidence.
(embodiment 1)
Prepare raw material powder.Raw material powder is 1.5 μm of average grain diameter of Al2O3Powder, 0.5 μm of average grain diameter of MgO powder
End, 1.0 μm of average grain diameter of SiO2Powder, 1.0 μm of average grain diameter of MnCO3Powder and 0.5 μm of average grain diameter of ZrO2Powder,
The MoO that 3.0 μm of average grain diameter3Powder.
By raw material powder in ratio (Al shown in following table 22O3Powder: 91.8 mass %, SiO2Powder: 3.3 mass %,
MnCO3Powder: 7.0 mass % (being calculated as 4.3 mass % by MnO conversion), MgO powder: 0.0 mass %, MoO3Powder: 0.5 matter
Measure %, ZrO2Powder: 0.2 mass %) mixing, obtain mixed-powder.In obtained mixed-powder, mixing is used as organic principle
Polyvinyl butyral, tertiary amine and phthalic acid ester (phthalic acid diisononyl esters: DINP), mixing, diffusion conduct
The IPA (isopropanol) and toluene of solvent modulates slurry, then, 60~270 μm of thickness of ceramic band is produced by scraper method.
By obtained ceramic band in 1260 DEG C of firing temperature (maximum temperature), H2+N2Forming gas atmosphere in be burnt into, produce
Ceramic matrix involved in embodiment 1.Conductor is formed by firing simultaneously.As ceramic matrix, make for confirming knot
First ceramic matrix of crystal phase and the second ceramic matrix for confirming bending strength.Embodiment explained below 2,3 and ratio
It is also the same compared with example 1~7.
(embodiment 2)
In raw material powder, make MnCO3Powder is 5.8 mass % (being calculated as 3.6 mass % by MnO conversion), makes ZrO2Powder
For 0.9 mass %, making firing temperature (maximum temperature) is 1340 DEG C, in addition to this, produces reality in the same manner as in the above embodiment 1
Apply ceramic matrix involved in example 2.
(embodiment 3)
In raw material powder, make SiO2Powder is 4.0 mass %, makes MnCO3Powder is 4.7 mass % (based on MnO conversion
For 2.9 mass %), makes 0.3 mass % of MgO powder, make MoO3Powder is 0.0 mass % (being not added with), makes ZrO2Powder is
1.0 mass %, making firing temperature (maximum temperature) is 1360 DEG C, in addition to this, produces implementation in the same manner as in the above embodiment 1
Ceramic matrix involved in example 3.
(embodiment 4)
In raw material powder, make Al2O3Powder is 94.0 mass %, makes SiO2Powder is 2.5 mass %, makes MnCO3Powder
For 4.1 mass % (being calculated as 2.5 mass % by MnO conversion), make ZrO2Powder is 0.5 mass %, makes the firing temperature (highest temperature
Degree) it is 1400 DEG C, in addition to this, ceramic matrix involved in embodiment 4 is produced in the same manner as in the above embodiment 1.
(comparative example 1)
In raw material powder, make SiO2Powder is 3.8 mass %, makes MnCO3Powder is 6.0 mass % (based on MnO conversion
For 3.7 mass %), make ZrO2Powder is 0.0 mass % (being not added with), and making firing temperature (maximum temperature) is 1360 DEG C, removes this
In addition, ceramic matrix involved in comparative example 1 is produced in the same manner as in the above embodiment 1.
(comparative example 2)
In raw material powder, make Al2O3Powder is 91.0 mass %, makes SiO2Powder is 4.0 mass %, makes MnCO3Powder
For 4.7 mass % (being calculated as 2.9 mass % by MnO conversion), makes 0.5 mass % of MgO powder, make MoO3Powder is 0.0 matter
It measures % (being not added with), makes ZrO2Powder is 0.0 mass % (being not added with), makes TiO2Powder is 1.0 mass %, makes firing temperature (most
High-temperature) it is 1330 DEG C, in addition to this, ceramic matrix involved in comparative example 2 is produced in the same manner as in the above embodiment 1.
(comparative example 3)
It is burnt into an atmosphere, in addition to this, ceramic base involved in comparative example 3 is produced in the same manner as comparative example 2
Body.In the comparative example 3, not instead of by and meanwhile firing form conductor, formed after firing.
(comparative example 4)
In raw material powder, make Al2O3Powder is 90.5 mass %, makes SiO2Powder is 5.0 mass %, makes MnCO3Powder
For 1.9 mass % (being calculated as 1.2 mass % by MnO conversion), makes 0.8 mass % of MgO powder, make MoO3Powder is 0.0 matter
It measures % (being not added with), makes ZrO2Powder is 0.8 mass %, makes TiO2Powder is 1.7 mass %, makes firing temperature (maximum temperature)
It is 1300 DEG C, in addition to this, produces ceramic matrix involved in comparative example 4 in the same manner as in the above embodiment 1.
(comparative example 5)
In raw material powder, make Al2O3Powder is 92.0 mass %, makes SiO2Powder is 4.0 mass %, makes MnCO3Powder
For 6.3 mass % (being calculated as 3.9 mass % by MnO conversion), makes 0.5 mass % of MgO powder, make MoO3Powder is 0.0 matter
It measures % (being not added with), makes ZrO2Powder is 0.0 mass % (being not added with), and making firing temperature (maximum temperature) is 1330 DEG C, removes this
In addition, ceramic matrix involved in comparative example 5 is produced in the same manner as in the above embodiment 1.
(comparative example 6)
In raw material powder, make Al2O3Powder is 91.0 mass %, makes SiO2Powder is 4.0 mass %, makes MnCO3Powder
For 4.7 mass % (being calculated as 2.9 mass % by MnO conversion), makes 0.5 mass % of MgO powder, make MoO3Powder is 0.0 matter
It measures % (being not added with), makes ZrO2Powder is 0.0 mass % (being not added with), makes Cr2O3Powder is 1.0 mass %, makes firing temperature
(maximum temperature) is 1300 DEG C, in addition to this, produces ceramic matrix involved in comparative example 6 in the same manner as in the above embodiment 1.
(comparative example 7)
In raw material powder, make Al2O3Powder is 91.0 mass %, makes SiO2Powder is 4.0 mass %, makes MnCO3Powder
For 4.7 mass % (being calculated as 2.9 mass % by MnO conversion), makes 0.5 mass % of MgO powder, make MoO3Powder is 0.0 matter
It measures % (being not added with), makes ZrO2Powder is 0.0 mass % (being not added with), makes Fe3O4Powder is 1.0 mass %, makes firing temperature
(maximum temperature) is 1300 DEG C, in addition to this, produces ceramic matrix involved in comparative example 7 in the same manner as in the above embodiment 1.
(evaluation)
The confirmation > of < crystalline phase
Each first ceramic matrix of Examples 1 to 4 and comparative example 1~7 is crushed, is identified by X-ray diffraction.
< bending strength >
4 bending strength tests based on JISR1601, at room temperature to each of Examples 1 to 4 and comparative example 1~7
Second ceramic matrix is measured.
< dielectric loss angle tangent >
It is measured under room temperature, frequency 2GHz based on JISC2565 using cavity resonance method.
< chipping incidence >
As shown in Figure 5A, polyelectron part substrate 60 is produced.Polyelectron part substrate 60 has being capable of transversely chip
Be divided into 23 multilayer boards 12, and can along longitudinal direction chip separation at 23 multilayer boards 12 size.Also that is, the polyelectron
Part substrate 60 have can obtain 23 × 23=529, width Lx as shown in Figure 5 B is 2.0mm, length Ly is 1.6mm, thickness
Degree t is the size of the multilayer board 12 of 0.4mm (the thickness tb:0.2mm of base portion 16).
The laminated body stage of polyelectron the part substrate 60 before firing upper surface in base portion 16 and following table as shown in Figure 5 C
Face is formed with the segmentation groove 62 (depth: 2 μm) for chip separation.
Then, it is pushed against with compression roller, chip separation is carried out to the polyelectron part substrate 60 for being formed with segmentation groove 62, point
After being cut into 529 multilayer boards 12, the segmentation end face of each multilayer board 12 is observed.In 4 segmentation end faces of 1 multilayer board 12
In at least one divide end face, be formed with 100 μm of diameter or more and 10 μm of depth or more pit or 100 μm of diameter or more
And in the case where the protrusion of 10 μm of height or more, it is evaluated as that chipping has occurred on the multilayer board 12.
Chipping incidence refers to: chip of the number of the multilayer board 12 of chipping relative to polyelectron part substrate 60 occurs
The ratio of segmentation number 529.Relative to 1 polyelectron part substrate 60, in the case where having 1 multilayer board 12 that chipping occurs,
Chipping incidence is 1/529=0.19%.
It in the present embodiment, is evaluated with 5 polyelectron part substrates 60, therefore, chipping incidence is (chipping to occur
The number of multilayer board 12)/(529 × 5).
The detailed content of Examples 1 to 4 and comparative example 1~7 is shown in table 2, shows the results of the evaluation table 3.
[table 2]
[table 3]
Al is removed as crystalline phase for Examples 1 to 42O3Other than phase, ZrO is only observed2Phase.In addition, bending strength
For 600MPa or more, dielectric loss angle tangent is 10 × 10- 4Below.Chipping incidence is lower than 0.15%.
On the other hand, for comparative example 1~7, chipping incidence is 0.15% or more.In addition, being observed as crystalline phase
To MnTiO3The dielectric loss angle tangent of the comparative example 2~4 of phase is larger.Wherein, it was further observed that Mn3Al2(SiO4)3The comparison of phase
The bending strength of example 4 is down to 500MPa.In addition, for only observing Al as crystalline phase2O3Comparative example 6 and 7, there is also Jie
The biggish tendency of electrical loss angle tangent.
It should be noted that ceramic matrix according to the present invention and its manufacturing method are not limited to above embodiment, do not taking off
Under the premise of present subject matter, it is of course possible to use various compositions.
Claims (6)
1. a kind of ceramic matrix, which is characterized in that
The crystalline phase of the ceramic matrix is with Al2O3It only include in addition to this ZrO for main crystalline phase2Crystalline phase,
The ceramic matrix includes: by Al2O3Conversion is calculated as the Al of 89.0~92.0 mass %, by SiO2Conversion is calculated as 2.0~
The Si of 5.0 mass %, by MnO conversion be calculated as 2.0~5.0 mass % Mn, by MgO conversion be calculated as 0~2.0 mass % Mg,
By ZrO2Conversion is calculated as the Zr of 0.05~2.0 mass %.
2. ceramic matrix according to claim 1, which is characterized in that
The bending strength of 4 based on the JISR1601 bending strength test measurement of the ceramic matrix is 600MPa or more.
3. ceramic matrix according to claim 1 or 2, which is characterized in that
The ceramic matrix is sintered in 1200~1400 DEG C of temperature.
4. a kind of manufacturing method of ceramic matrix, is with Al2O3For main crystalline phase, in addition to this only comprising ZrO2The pottery of crystalline phase
The manufacturing method of porcelain basal body, which is characterized in that comprise the following steps:
The formed body production process of formed body is made, the formed body contains the Al of 89.0~92.0 mass %2O3Powder, 2.0~
The SiO of 5.0 mass %2The MnCO of powder, 3.2~8.1 mass %3Powder, the MgO powder of 0~2.0 mass %, 0.05~2.0
The ZrO of quality %2Powder, wherein the MnCO3Powder is calculated as 2.0~5.0 mass % by MnO conversion,
The firing process that the formed body is burnt at 1200~1400 DEG C.
5. the manufacturing method of ceramic matrix according to claim 4, which is characterized in that
It further include the process that the conductor layer containing metal is formed on the formed body,
The formed body for being formed with the conductor layer is burnt into the firing process.
6. the manufacturing method of ceramic matrix according to claim 4 or 5, which is characterized in that
The firing process hydrogen content be 5% or more hydrogen and nitrogen forming gas in carry out.
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| JP7108704B2 (en) * | 2018-10-22 | 2022-07-28 | 日本碍子株式会社 | ceramic base |
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| CN1138565A (en) * | 1995-03-17 | 1996-12-25 | 陶瓷标记技术公司 | Alumina-based ceramic for sintering, method of manufacture and rubbing parts obtained thereby |
| CN101107205A (en) * | 2005-01-27 | 2008-01-16 | 京瓷株式会社 | Composite ceramic and method for producing same |
| CN101962289A (en) * | 2009-07-21 | 2011-02-02 | 财团法人工业技术研究院 | Ceramic powder composition and base plate of photovoltaic device using same |
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| JPH03218967A (en) * | 1989-11-06 | 1991-09-26 | Osaka Cement Co Ltd | High-strength alumina-zirconia-based ceramics sintered body |
| JP2004119735A (en) * | 2002-09-26 | 2004-04-15 | Kyocera Corp | Connected substrate, its manufacturing method and ceramic package |
| JP4578076B2 (en) * | 2003-08-07 | 2010-11-10 | 日本特殊陶業株式会社 | Alumina sintered body and IC substrate |
| JP3993619B2 (en) * | 2005-07-06 | 2007-10-17 | 株式会社住友金属エレクトロデバイス | Ceramic circuit board assembly |
| JP2008024583A (en) * | 2006-06-23 | 2008-02-07 | Nippon Soken Inc | Alumina composite sintered body, evaluation method thereof and spark plug |
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| CN1138565A (en) * | 1995-03-17 | 1996-12-25 | 陶瓷标记技术公司 | Alumina-based ceramic for sintering, method of manufacture and rubbing parts obtained thereby |
| CN101107205A (en) * | 2005-01-27 | 2008-01-16 | 京瓷株式会社 | Composite ceramic and method for producing same |
| CN101962289A (en) * | 2009-07-21 | 2011-02-02 | 财团法人工业技术研究院 | Ceramic powder composition and base plate of photovoltaic device using same |
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