WO2018139209A1 - Joining material and joined body - Google Patents
Joining material and joined body Download PDFInfo
- Publication number
- WO2018139209A1 WO2018139209A1 PCT/JP2018/000565 JP2018000565W WO2018139209A1 WO 2018139209 A1 WO2018139209 A1 WO 2018139209A1 JP 2018000565 W JP2018000565 W JP 2018000565W WO 2018139209 A1 WO2018139209 A1 WO 2018139209A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bonding
- oxide
- joined body
- glass
- additive
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 197
- 239000000654 additive Substances 0.000 claims abstract description 53
- 230000000996 additive effect Effects 0.000 claims abstract description 50
- 239000000075 oxide glass Substances 0.000 claims abstract description 28
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 27
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 26
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 19
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000002585 base Substances 0.000 claims description 47
- 239000004065 semiconductor Substances 0.000 claims description 19
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 31
- 238000001465 metallisation Methods 0.000 abstract description 7
- 239000004020 conductor Substances 0.000 abstract 1
- 238000005476 soldering Methods 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 64
- 239000000203 mixture Substances 0.000 description 41
- 239000010410 layer Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- 239000002245 particle Substances 0.000 description 12
- 229910000679 solder Inorganic materials 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 206010040844 Skin exfoliation Diseases 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005219 brazing Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- -1 holsterite Chemical compound 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052752 metalloid Inorganic materials 0.000 description 3
- 150000002738 metalloids Chemical class 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 238000005382 thermal cycling Methods 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- 238000011156 evaluation Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000012925 reference material Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 229910052644 β-spodumene Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- 230000009467 reduction Effects 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C03C8/24—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
-
- 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
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
Definitions
- the present invention relates to a bonding material containing a glass composition and a bonded body using the bonding material.
- ⁇ Microdevices used in electronic equipment such as electrical and electronic equipment, LED lighting, and semiconductor modules have joints where ceramic, semiconductor, glass, and metal base materials are joined to another base material.
- these joining portions are usually joined by epoxy resin, acrylic resin, or the like.
- the base materials are usually joined by a solder material or a brazing material.
- a brazing material containing an active metal such as Ti (titanium) or Al (aluminum) can be joined to ceramics without being metallized, but treatment at a high temperature of 800 ° C. is necessary. From the viewpoint of simplification of the process and cost reduction, there is a strong demand for a bonding material that can bond base materials to each other at a low temperature equivalent to that of a solder material without metallization.
- Patent Document 1 discloses a lead-free glass composition containing Bi 2 O 3 and SiO 2 as main components and having a softening point of 570 ° C. or lower, TiO 2 , Al 2 O 3 , and ZrO 2 for maintaining chemical stability. , A bonding material containing a filler material such as SiO 2 is disclosed.
- Patent Document 2 discloses a sealing material containing a glass composition containing SiO 2 as a main component and a filler for suppressing interfacial peeling due to thermal expansion.
- fillers alumina, cordierite, silica, zircon, aluminum titanate, holsterite, mullite, ⁇ -eucryptite, ⁇ -spodumene and the like are disclosed.
- Patent Document 3 discloses a bonding material that can bond base materials such as ceramics, semiconductors, and glass at a processing temperature of a solder material without metallization.
- a bonding material a bonding material containing a glass composition mainly composed of V (vanadium) and Te (tellurium) and Ag (silver) particles is used.
- the bonding material or sealing material disclosed in Patent Documents 1 and 2 does not mention bonding of base materials made of a metal or a semiconductor forming a natural oxide film.
- Patent Document 3 discloses that the bonding material can bond base materials such as ceramics and semiconductors without metallization.
- base materials such as ceramics and semiconductors
- application to a base material made of a metal, semimetal or semiconductor that forms a natural oxide film on the surface has not been sufficiently studied. Therefore, a bonding material that can further improve the bonding strength when bonding a base material made of metal, metalloid, or semiconductor that forms a natural oxide film on the surface is expected.
- An object of the present invention is to provide a technique capable of joining a base material made of a metal, a semimetal or a semiconductor forming a natural oxide film at a low temperature of a solder material without a metallization process and obtaining a high joint strength. is there.
- a bonding material according to the present invention includes an oxide glass containing V and Te and an additive, and the additive is Si powder or silicon nitride powder. It is characterized by that.
- a base material made of a metal, a semimetal or a semiconductor that forms a natural oxide film and another base material can be joined at a low temperature such as a solder material without metallization, and a high joining strength can be obtained. Can be provided.
- FIG. 1 It is sectional drawing which shows typically the structure of the conjugate
- FIG. It is an X-ray-diffraction result of the peeling surface at the side of the Si substrate of the joined body according to Example 1. It is an X-ray-diffraction result of the peeling surface at the side of the joining material of the joined body which concerns on Example 1.
- FIG. It is a figure which shows the relationship between the addition amount of the additive in the joining material which concerns on an Example, and a comparative example, and joining strength.
- the bonding material according to the present invention includes an oxide glass containing V and Te, and an additive.
- the oxide glass is preferably lead-free (containing no lead, lead-free) in consideration of the environment.
- lead-free means that prohibited substances in the RoHS Directive (Restriction of Hazardous Substance: effective July 1, 2006) are contained within a specified value range or less.
- the oxide glass is a low-melting glass and preferably softens and flows at 600 ° C. or lower.
- the oxide glass preferably contains Ag in addition to V and Te.
- Ag the characteristic temperature of the glass is lowered.
- the glass transition temperature is about 160 to 270 ° C.
- the softening and flowing temperature is 210 to 350 ° C.
- the temperature at which the glass crystallizes and the crystal melts is about 350 to 420 ° C.
- the bonding layer can be made to conduct heat conduction and electric conduction.
- oxide glass contains V, Te, and Ag in total 80 mol% or more in conversion of an oxide. That is, it is preferable to satisfy V 2 O 5 + TeO 2 + Ag 2 O ⁇ 80 mol%. By satisfying this relationship, it is possible to achieve both a low glass transition temperature, a softening flow temperature, and a stable glass structure.
- the content of V 2 O 5 in the oxide glass is 10 mol% or more and 30 mol% or less, the content of TeO 2 is 30 mol% or more and 50 mol% or less, and the content of Ag 2 O is 20 mol% or more and 40 mol%. % Or less is preferable.
- the oxide glass may further contain at least one element of Ba, P, W, La, and alkali metal.
- the oxide glass has a high melting point of the material after crystallization or the material after change, the heat resistance of bonding is improved.
- the material after crystallization or the material after change may be brittle and may reduce the bonding strength. In such a case, by containing these components, the glass structure is further stabilized, and a decrease in bonding strength can be suppressed.
- the oxide glass preferably has a glass transition temperature of 200 ° C. or lower.
- bonding can be performed at a temperature similar to that of the solder material.
- the additive is Si powder or silicon nitride powder. These may be used alone or in combination.
- the Si powder or silicon nitride powder reacts with the natural oxide film formed on the metal, metalloid and semiconductor forming the natural oxide film and its lower layer at the time of bonding, and promotes reconfiguration of the bonding interface at the time of cooling. As a result, high bonding strength can be obtained.
- Si powder or silicon nitride powder when Si powder or silicon nitride powder is used as an additive, higher bonding strength can be obtained than when metal particles such as Ag particles are used as an additive. This is because metal particles such as Ag particles have a large coefficient of thermal expansion, cannot relax the thermal expansion of glass during heat treatment and cooling, and are difficult to relieve stress.
- the thermal expansion coefficient of the base material and the bonding material is large, thermal stress is generated at the interface between the base material and the bonding material, and high bonding strength may not be obtained. Since the Si powder or the silicon nitride powder has a lower thermal expansion coefficient than the oxide glass containing V and Te, the difference in the thermal expansion coefficient between the bonding material and the base material can be reduced. Since the effect of reducing thermal expansion depends on the particle diameter of the additive to be added, the particle diameter of the additive is preferably 100 nm or more and 100 ⁇ m or less. By making the particle diameter of the additive 100 nm or more, the effect of relaxation of thermal expansion by the additive can be improved. Moreover, the reaction surface area of an additive can be earned by making the particle diameter of an additive into 100 micrometers or less, and the reactivity with a base material can be maintained.
- the content of the oxide glass with respect to the total volume of the oxide glass and the additive is preferably more than 20% by volume and less than 80% by volume, more preferably 30% by volume or more and 70% by volume or less, and 40% by volume or more. More preferably, it is 60 volume% or less.
- An additive other than Si powder or silicon nitride powder may be further added to the bonding material.
- the amount of gas containing oxygen and nitrogen generated during bonding varies depending on the type of additive. By using different additives depending on the types of base materials to be joined, higher joint strength can be obtained.
- Examples of the method of bonding the base material using the bonding material include the following two methods.
- the base materials are joined to each other by applying a paste prepared by adding a solvent to a joining material containing a glass composition containing V and Te and an additive, and heating the paste.
- a solvent used for pasting include water, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, methanol, ethanol, propanol, ethylene glycol, glycerin, dimethyl sulfoxide, tetrahydrofuran, and terpineol.
- butylhydroxyanisole Since the paste needs a certain viscosity, terpineol and butylhydroxyanisole are particularly preferable. These solvents may be used alone or in combination.
- a polymer additive such as polyvinylidene fluoride (PVdF) is further added to a bonding material including a glass composition containing V and Te and an additive, thereby forming a sheet.
- the joining material formed into a sheet is sandwiched between base materials and joined by heating.
- polymeric additives such as PVdF include acrylic resins, urethane resins, phenolic resins, imide resins, glyoxal resins, butadiene resins, methacrylic resins, fluorine resins, styrene resins, Examples thereof include ethylene resins. These resins may be used alone or in combination. When such a polymer is mixed, the influence of stress due to the difference in thermal expansion coefficient of the base material can be alleviated, and a decrease in bonding strength can be suppressed.
- the polymer When a polymer additive is added to the glass composition and the additive, and then formed into a highly flexible sheet, the polymer is added to the total volume% of the glass composition and the additive.
- the addition amount of the agent is preferably 5% by volume or more and 70% by volume or less.
- the atmosphere at the time of bonding includes air, oxygen gas, nitrogen gas, argon gas, etc., inert atmosphere, hydrogen gas reducing atmosphere, etc. In any case, high bonding strength can be obtained. It is preferable that the atmosphere at the time of joining is properly used depending on the type and use of the substrates to be joined.
- the heating method at the time of joining is generally heating in a thermostatic chamber.
- heating can be performed by converting light energy into heat energy by laser irradiation.
- the bonding material is heated to a temperature equal to or higher than the crystallization temperature of the oxide glass to crystallize the oxide glass and then melt. It is preferable to join by. This is because by obtaining a higher fluidity than the softening flow of the glass by melting, the contactability and adhesion of the glass and additive to the bonding interface are improved and higher reactivity is obtained. However, it is not necessary to crystallize the glass if it has high softening fluidity without crystallizing and melting the glass.
- the heating temperature at the time of joining is preferably about the temperature at which the crystallized oxide glass melts.
- the heating temperature is preferably 320 to 420 ° C.
- the load during bonding is preferably 0.05 kg / cm 2 or more and 1.0 kg / cm 2 or less.
- the joined body 1 includes a first base material 101 made of a metal, a semimetal, or a semiconductor that forms a natural oxide film, a joining layer 102, and a second base material 103.
- the first substrate may be a metal, a semimetal, or a semiconductor that forms a natural oxide film, and the first substrate includes an oxide film layer.
- the metal, metalloid and semiconductor forming the natural oxide film are Ti (titanium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Zr (zirconium) Nb (niobium), Mo (molybdenum), W (tungsten), Ag (silver), Si (silicon), Al (aluminum), Bi (bismuth), Ge (germanium), Sn (Tin), In (indium) Pt (platinum), Au (gold), or an alloy containing these.
- the bonding layer 102 includes an oxide containing (vanadium) and Te (tellurium) and an additive, and the additive contains Si or silicon nitride.
- the oxide 105 containing V and Te and the additive (Si or silicon nitride) 104 are preferably dispersed as shown in FIG.
- FIG. 2 shows a form in which the additive is dispersed in the oxide, the oxide may be dispersed in the additive. Since the oxide and the additive are dispersed, a decrease in bonding strength can be suppressed.
- the ratio of the oxide containing V and Te to the total volume of the oxide containing V and Te and the additive is preferably more than 20% by volume and less than 80% by volume, and is 30% by volume or more and 70% by volume or less. It is more preferable that it is 40 volume% or more and 60 volume% or less.
- the bonding layer 102 preferably has voids.
- the thermal expansion coefficients of the first base material 101 or the second base material 103 and the bonding layer are greatly different, there is a risk of peeling due to a thermal cycle or the like.
- By dispersing the voids in the bonding layer 102 it is possible to relax the thermal stress and increase the resistance to thermal cycling.
- the proportion of voids in the bonding layer is preferably 10% by volume or less. By setting the ratio of the voids to 10% by volume or less, it is possible to suppress a decrease in bonding strength due to a decrease in the contact area between the base material and the bonding material.
- the size of the gap is preferably approximately 10 nm to 10 ⁇ m. By setting the size of the gap to 10 nm or more, the effect of stress relaxation due to the gap can be sufficiently obtained. By setting the size of the gap to 10 ⁇ m or less, high bonding strength can be obtained without impeding contact between the bonding material and the substrate.
- the oxide containing V and Te may have an amorphous phase. Note that although oxide glass is used as the bonding material, the oxide containing V and Te contained in the bonding layer of the bonded body does not need to maintain a glass state.
- the oxide containing V and Te may be in a glass state or may be crystallized. Moreover, it may react with the additive in a base material or a joining layer, and may change into another substance.
- the oxide phase preferably contains Ag in addition to V and Te, and more preferably contains V, Te and Ag in total 80 mol% or more in terms of oxide.
- the oxide phase preferably contains at least one of Ba (barium), W (tungsten), La (lanthanum), P (phosphorus), and an alkali metal. By including these in the oxide phase, it is possible to suppress a decrease in bonding strength.
- the material of the second base material 103 is not particularly limited, such as metal, glass, and ceramics.
- the metal include, for example, base materials containing Cu (copper), Ni (nickel), Co (cobalt), Fe (iron), Al (aluminum), and the like, or alloys thereof.
- the glass include boric acid glass, silicic acid glass, phosphoric acid glass, and vanadium glass.
- ceramics include aluminum oxide, aluminum nitride, silicon nitride, and silicon carbide. In general, since metal, glass, ceramics, and semiconductor have different coefficients of thermal expansion, the joint surface is vulnerable to thermal cycling.
- gas is generated at the time of bonding by Si, silicon nitride, or the like contained in the bonding material, and voids are formed in the bonding layer by the generated gas. Since the large thermal stress due to the difference in thermal expansion coefficient is relieved by the voids, a bonded body resistant to thermal cycling can be obtained.
- the second base material 103 includes an oxide film layer.
- a modified surface layer is also included in the base material.
- the structure of the bonded body can be confirmed visually, and the composition and structure of the bonding layer and the bonding interface between the base material and the bonding layer are Auger electron spectroscopy, X-ray photoelectron spectroscopy, fluorescent X-ray analysis, X-ray diffraction analysis, and electron This can be confirmed by microscopic observation.
- the glass composition used for the bonding material was prepared as follows.
- the starting material was weighed to a predetermined molar ratio. Specifically, 20.5 mol% of V 2 O 5 , 39.5 mol% of TeO 2 , 32.5 mol% of Ag 2 O, 5.0 mol% of WO 3 , 2 of La 2 O 3 .5 mol%.
- oxide powder purity: 99.9% or more
- the starting materials were mixed and placed in a crucible. The mixture was mixed until the color was visually uniform, and the crucible containing the mixed powder was placed in a glass melting furnace, heated and melted. About 10 ° C./min.
- the glass was melted at a set temperature of 750 ° C. and held for 1 hour while stirring. Thereafter, the crucible was removed from the glass melting furnace, and the glass was poured into a plate that had been heated to 150 ° C. in advance, and cooled. The glass cooled to room temperature was coarsely pulverized to produce a glass composition powder. This was designated as Glass Composition A.
- ⁇ Bonding material> The glass composition A and Si powder were weighed so that the volume ratio was 50% by volume, and mixed in an agate mortar until the color became uniform visually to obtain a mixed powder of the bonding material. Thereafter, 0.2 g of the mixed powder of the bonding material was put into a 10 mm ⁇ die, a load of 1 ton was applied, and the mixture was held for 1 minute to produce a bonding material pellet. The thermal characteristics of this bonding material were evaluated with a differential thermal analyzer.
- the differential thermal analyzer is a method of measuring the temperature difference between the sample and the reference material as a function of temperature while changing the temperature of the sample and the reference material according to a certain program.
- FIG. 3 shows the thermal property evaluation results of the bonding material.
- the endothermic behavior of the glass transition point due to the glass composition was observed near 189 ° C. Although the softening point was not clearly clarified, an exothermic behavior due to crystallization of the glass composition was observed from 330 ° C., and a sharp endothermic behavior due to the melting point of the glass composition crystallized around 377 ° C. was confirmed. It was done.
- a 10 mm square Si substrate and an aluminum oxide substrate were used as the base material.
- a bonding material pellet was placed on an aluminum oxide substrate, and a Si substrate was placed on top so as to sandwich the pellet to obtain a precursor of a joined body.
- a weight made of SUS was placed on the precursor of the joined body so that the load would be 0.25 kg / cm 2, and it was put into an electric furnace. Then, it heated up to 400 degreeC with the temperature increase rate of 10 degree-C / min, hold
- the bonding strength of this bonded body was measured by applying a shear load parallel to the bonding surface to the Si chip. Moreover, the crystal structure of the peeled Si substrate surface and the peeled surface of the bonding material was evaluated by X-ray diffraction measurement.
- FIG. 4 shows the X-ray diffraction results of the peeled Si substrate surface
- FIG. 4 shows the X-ray diffraction results of the peeled Si substrate surface
- FIG. 5 shows the X-ray diffraction results of the peeled surface of the bonding material. From FIG. 4, a peak derived from the Si powder in the bonding material, a peak derived from the (100) orientation plane of the Si substrate, and a peak derived from Ag precipitated from the glass composition were confirmed. Moreover, from FIG. 5, the peak derived from the aluminum oxide substrate, the peak derived from Ag deposited from the glass composition, and the peak of the Si powder as the additive were confirmed. From these results, it was found that no distinct heterogeneous phase was formed at the peel interface after bonding.
- a bonding material was produced in the same procedure as in Example 1 except that the content of Si powder in the bonding material was changed to 20% by volume, and a bonded body was manufactured using the bonding material.
- a bonding material was produced in the same procedure as in Example 1 except that the content of Si powder in the bonding material was changed to 30% by volume, and a bonded body was manufactured using the bonding material.
- a bonding material was produced in the same procedure as in Example 1 except that the content of Si powder in the bonding material was changed to 40% by volume, and a bonded body was manufactured using the bonding material.
- a bonding material was produced in the same procedure as in Example 1 except that the content of Si powder in the bonding material was changed to 60% by volume, and a bonded body was manufactured using the bonding material.
- a bonding material was produced in the same procedure as in Example 1 except that the content of Si powder in the bonding material was changed to 70% by volume, and a bonded body was manufactured using the bonding material.
- a bonding material was produced in the same procedure as in Example 1 except that the content of Si powder in the bonding material was changed to 80% by volume, and a bonded body was manufactured using the bonding material.
- a bonding material was prepared in the same procedure as in Example 1 except that the Si powder in the bonding material was changed to Si 3 N 4 powder, and a bonded body was manufactured using the bonding material.
- the particle diameter of the used Si 3 N 4 powder was 50 ⁇ m or less.
- a bonding material was prepared in the same procedure as in Example 8 except that the content of Si 3 N 4 powder in the bonding material was changed to 20% by volume, and a bonded body was manufactured using the bonding material.
- a joining material was produced in the same procedure as in Example 8 except that the content of Si 3 N 4 powder in the joining material was changed to 30% by volume, and a joined body was produced using the joining material.
- a joining material was produced in the same procedure as in Example 8 except that the content of Si 3 N 4 powder in the joining material was changed to 40% by volume, and a joined body was produced using the joining material.
- a joining material was produced in the same procedure as in Example 8 except that the content of Si 3 N 4 powder in the joining material was changed to 60% by volume, and a joined body was produced using the joining material.
- a joining material was produced in the same procedure as in Example 8 except that the content of Si 3 N 4 powder in the joining material was changed to 70% by volume, and a joined body was produced using the joining material.
- a joining material was produced in the same procedure as in Example 8 except that the content of Si 3 N 4 powder in the joining material was changed to 80% by volume, and a joined body was produced using the joining material.
- a bonding material was prepared in the same procedure as in Example 1 except that the glass composition A in the bonding material was changed to the glass composition B, and a bonded body was manufactured using the bonding material.
- the composition of the glass composition B is as follows: V 2 O 5 20.0 mol%, TeO 2 37.5 mol%, Ag 2 O 35.0 mol%, BaO 5.0 mol%, WO 3 2 0.0 mol% and La 2 O 3 were 0.5 mol%.
- a bonding material was produced in the same procedure as in Example 8 except that the glass composition in the bonding material was changed to the glass composition B, and a bonded body was manufactured using the bonding material.
- Example 1 A joining material was produced in the same procedure as in Example 1 except that no Si powder was added to the joining material, and a joined body was produced using the joining material.
- Example 2 A joining material was produced in the same procedure as in Example 1 except that only Sn particles were used without adding a glass composition and Si powder as a joining material, and a joined body was produced using the joining material.
- Example 3 A bonding material was prepared in the same procedure as in Example 1 except that only the Sn 3.5 mass% Ag particles were used without adding the glass composition and Si powder as the bonding material, and the bonded body was formed using the bonding material. Manufactured.
- Example 4 A joining material was produced in the same procedure as in Example 1 except that only Ag particles were used without adding a glass composition and Si powder as a joining material, and a joined body was produced using the joining material.
- Example 5 A joining material was produced in the same procedure as in Example 1 except that the Si powder in the joining material was changed to SiO 2 powder, and a joined body was produced using the joining material.
- Example 6 A bonding material was prepared in the same procedure as in Example 1 except that the Si powder in the bonding material was changed to Ag powder, and a bonded body was manufactured using the bonding material.
- Fig. 6 shows the relationship between the amount of additive added in the bonding material and the bonding strength. Regardless of whether Si powder or silicon nitride powder is used as the additive, the additive is 20% by volume (Examples 2 and 9) and 80% by volume (Examples 7 and 14) with respect to the glass composition. When added, the bonding strength was low. On the other hand, in Examples 1, 3 to 6, 8, 10 to 13, 15, and 16 in which the additive is added in an amount of 30 to 70% by volume with respect to the glass composition, the conventional bonding material shown in the comparative example In comparison, it was revealed that the bonding strength was extremely high.
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Abstract
The purpose of the present invention is to provide a technique whereby a substrate, said substrate comprising a metal, a semimetal or a conductor capable of forming a native oxide film, can be joined at such a low temperature as the temperature of a soldering material without carrying out a metallization treatment and thus a high joining strength can be obtained. To achieve this purpose, the joining material according to the present invention, which comprises an oxide glass containing V and Te and an additive material, is characterized in that the additive material is an Si powder or a silicon nitride powder.
Description
本発明は、ガラス組成物を含む接合材、及びその接合材を用いた接合体に関する。
The present invention relates to a bonding material containing a glass composition and a bonded body using the bonding material.
電気電子機器、ＬＥＤ照明、半導体モジュール等の電子機器類に使われるマイクロデバイスには、セラミックス、半導体、ガラス、金属の基材を別の基材と接合する接合箇所が存在する。これらの接合箇所が熱流や電流経路を兼ねない単純な接合の場合は、通常、エポキシ樹脂、アクリル樹脂などによって接合される。一方で、接合箇所が熱流や電流経路を兼ねる場合は、基材同士は通常、はんだ材やろう材によって接合される。
¡Microdevices used in electronic equipment such as electrical and electronic equipment, LED lighting, and semiconductor modules have joints where ceramic, semiconductor, glass, and metal base materials are joined to another base material. In the case of simple joining that does not serve as a heat flow or a current path, these joining portions are usually joined by epoxy resin, acrylic resin, or the like. On the other hand, when the joining portion also serves as a heat flow and a current path, the base materials are usually joined by a solder material or a brazing material.
はんだ材を用いてセラミックス、半導体、ガラスなどを強固に接合する場合は、その表面をメタライズ処理する必要がある。Ｔｉ（チタン）やＡｌ（アルミニウム）などの活性金属を含むろう材ではメタライズ処理せずにセラミックスの接合が可能であるが、８００℃の高温での処理が必要である。工程の簡略化、及びコスト低減の観点から、メタライズ処理無しに、はんだ材と同等の低温で、基材同士を接合できる接合材が切望されている。
When using a solder material to firmly bond ceramics, semiconductors, glass, etc., the surface must be metallized. A brazing material containing an active metal such as Ti (titanium) or Al (aluminum) can be joined to ceramics without being metallized, but treatment at a high temperature of 800 ° C. is necessary. From the viewpoint of simplification of the process and cost reduction, there is a strong demand for a bonding material that can bond base materials to each other at a low temperature equivalent to that of a solder material without metallization.
接合材としては、はんだ材やろう材のほかに、ガラス組成物の適用が検討されている。
As a bonding material, in addition to solder and brazing materials, application of glass compositions is being studied.
特許文献１には、Ｂｉ２Ｏ３とＳｉＯ２を主成分とし、５７０℃以下の軟化点を有する無鉛ガラス組成物と、化学的安定性を保つためのＴｉＯ２、Ａｌ２Ｏ３、ＺｒＯ２、ＳｉＯ２などのフィラー材と、を含有する接合材が開示されている。
Patent Document 1 discloses a lead-free glass composition containing Bi 2 O 3 and SiO 2 as main components and having a softening point of 570 ° C. or lower, TiO 2 , Al 2 O 3 , and ZrO 2 for maintaining chemical stability. , A bonding material containing a filler material such as SiO 2 is disclosed.
特許文献２には、ＳｉＯ２を主成分としたガラス組成物と、熱膨張による界面剥離を抑制するためのフィラーと、を含む封着材料が開示されている。フィラーとして、アルミナ、コージェライト、シリカ、ジルコン、チタン酸アルミニウム、ホルステライト、ムライト、β－ユークリプタイト、β－スポジューメンなどが開示されている。
Patent Document 2 discloses a sealing material containing a glass composition containing SiO 2 as a main component and a filler for suppressing interfacial peeling due to thermal expansion. As fillers, alumina, cordierite, silica, zircon, aluminum titanate, holsterite, mullite, β-eucryptite, β-spodumene and the like are disclosed.
特許文献３には、メタライズ処理せずに、セラミックス、半導体、ガラスなどの基材をはんだ材程度の処理温度で接合可能な接合材が開示されている。接合材としてＶ（バナジウム）とＴｅ（テルル）を主成分としたガラス組成物と、Ａｇ（銀）粒子とを含む接合材を用いている。
Patent Document 3 discloses a bonding material that can bond base materials such as ceramics, semiconductors, and glass at a processing temperature of a solder material without metallization. As a bonding material, a bonding material containing a glass composition mainly composed of V (vanadium) and Te (tellurium) and Ag (silver) particles is used.
特許文献１及び２に開示された接合材又は封着材料は、自然酸化膜を形成する金属又は半導体からなる基材の接合については言及されていない。
The bonding material or sealing material disclosed in Patent Documents 1 and 2 does not mention bonding of base materials made of a metal or a semiconductor forming a natural oxide film.
特許文献３の接合材は、メタライズ処理せずに、セラミックス、半導体等の基材を接合可能であることが開示されている。しかしながら、表面に自然酸化膜を形成する金属、半金属又は半導体からなる基材への適用については十分に検討されていない。そのため、表面に自然酸化膜を形成する金属、半金属又は半導体からなる基材を接合した際に、接合強度をさらに向上できる接合材が期待される。
Patent Document 3 discloses that the bonding material can bond base materials such as ceramics and semiconductors without metallization. However, application to a base material made of a metal, semimetal or semiconductor that forms a natural oxide film on the surface has not been sufficiently studied. Therefore, a bonding material that can further improve the bonding strength when bonding a base material made of metal, metalloid, or semiconductor that forms a natural oxide film on the surface is expected.
このように、自然酸化膜を形成する金属、半金属又は半導体から成る基材をメタライズ処理無しに、はんだ材と同等の低温で接合でき、かつ高い接合強度が得られる接合材および接合方法は見出されていない。
As described above, there is no need for a bonding material and a bonding method that can bond a base material made of a metal, semi-metal, or semiconductor that forms a natural oxide film at a low temperature equivalent to that of a solder material without metallizing, and that can provide high bonding strength. It has not been issued.
本発明の目的は、自然酸化膜を形成する金属、半金属又は半導体からなる基材を、メタライズ処理無しに、はんだ材程度の低温で接合でき、高い接合強度が得られる技術を提供することにある。
An object of the present invention is to provide a technique capable of joining a base material made of a metal, a semimetal or a semiconductor forming a natural oxide film at a low temperature of a solder material without a metallization process and obtaining a high joint strength. is there.
上記課題を解決するために本発明に係る接合材料は、Ｖ及びＴｅを含む酸化物ガラスと、添加材と、を含み、添加材はＳｉ粉末又は窒化ケイ素粉末であることを特徴とするであることを特徴とする。
In order to solve the above problems, a bonding material according to the present invention includes an oxide glass containing V and Te and an additive, and the additive is Si powder or silicon nitride powder. It is characterized by that.
本発明によれば、自然酸化膜を形成する金属、半金属又は半導体からなる基材と他の基材をメタライズ処理無しにはんだ材程度の低温で接合でき、かつ高い接合強度が得られる接合材を提供することができる。
According to the present invention, a base material made of a metal, a semimetal or a semiconductor that forms a natural oxide film and another base material can be joined at a low temperature such as a solder material without metallization, and a high joining strength can be obtained. Can be provided.
以下、図面等を用いて、本発明の実施形態について説明する。以下の説明は本発明の内容の具体例を示すものであり、本発明がこれらの説明に限定されるものではなく、本明細書に開示される技術的思想の範囲内において当業者による様々な変更および修正が可能である。また、本発明を説明するための全図において、同一の機能を有するものは、同一の符号を付け、その繰り返しの説明は省略する場合がある。
Hereinafter, embodiments of the present invention will be described with reference to the drawings. The following description shows specific examples of the contents of the present invention, and the present invention is not limited to these descriptions. Various modifications by those skilled in the art are within the scope of the technical idea disclosed in this specification. Changes and modifications are possible. In all the drawings for explaining the present invention, components having the same function are denoted by the same reference numerals, and repeated description thereof may be omitted.
＜接合材＞
本発明に係る接合材は、Ｖ及びＴｅを含む酸化物ガラスと、添加材と、を含む。酸化物ガラスは、環境への配慮から無鉛（鉛を含まないもの、鉛フリー）であることが好ましい。ここで、無鉛とは、ＲｏＨＳ指令（Ｒｅｓｔｒｉｃｔｉｏｎ ｏｆ Ｈａｚａｒｄｏｕｓ Ｓｕｂｓｔａｎｃｅ：２００６年７月１日施行）における禁止物質を指定値以下の範囲で含有することを容認するものとする。酸化物ガラスは低融点ガラスであり、６００℃以下で軟化流動することが好ましい。 <Bonding material>
The bonding material according to the present invention includes an oxide glass containing V and Te, and an additive. The oxide glass is preferably lead-free (containing no lead, lead-free) in consideration of the environment. Here, lead-free means that prohibited substances in the RoHS Directive (Restriction of Hazardous Substance: effective July 1, 2006) are contained within a specified value range or less. The oxide glass is a low-melting glass and preferably softens and flows at 600 ° C. or lower.
本発明に係る接合材は、Ｖ及びＴｅを含む酸化物ガラスと、添加材と、を含む。酸化物ガラスは、環境への配慮から無鉛（鉛を含まないもの、鉛フリー）であることが好ましい。ここで、無鉛とは、ＲｏＨＳ指令（Ｒｅｓｔｒｉｃｔｉｏｎ ｏｆ Ｈａｚａｒｄｏｕｓ Ｓｕｂｓｔａｎｃｅ：２００６年７月１日施行）における禁止物質を指定値以下の範囲で含有することを容認するものとする。酸化物ガラスは低融点ガラスであり、６００℃以下で軟化流動することが好ましい。 <Bonding material>
The bonding material according to the present invention includes an oxide glass containing V and Te, and an additive. The oxide glass is preferably lead-free (containing no lead, lead-free) in consideration of the environment. Here, lead-free means that prohibited substances in the RoHS Directive (Restriction of Hazardous Substance: effective July 1, 2006) are contained within a specified value range or less. The oxide glass is a low-melting glass and preferably softens and flows at 600 ° C. or lower.
酸化物ガラスは、Ｖ、Ｔｅの他にＡｇを含むことが好ましい。Ａｇを含むことにより、ガラスの特性温度が低温化する。具体的には、ガラス転移点温度が１６０～２７０℃程度、軟化流動する温度が２１０～３５０℃、ガラスが結晶化し、その結晶が融解する温度が３５０～４２０℃程度となる。その結果、低温での接合が可能となる。また、ガラス組成物からＡｇが析出した場合、接合層に熱伝導と電気伝導を担わせることができる。
The oxide glass preferably contains Ag in addition to V and Te. By including Ag, the characteristic temperature of the glass is lowered. Specifically, the glass transition temperature is about 160 to 270 ° C., the softening and flowing temperature is 210 to 350 ° C., the temperature at which the glass crystallizes and the crystal melts is about 350 to 420 ° C. As a result, bonding at a low temperature is possible. Moreover, when Ag precipitates from the glass composition, the bonding layer can be made to conduct heat conduction and electric conduction.
また、酸化物ガラスは、Ｖ、Ｔｅ、Ａｇを酸化物換算で合計８０モル％以上含むことが好ましい。すなわち、Ｖ２Ｏ５＋ＴｅＯ２＋Ａｇ２Ｏ≧８０モル％を満たすことが好ましい。この関係を満たすことにより、低いガラス転移点温度、軟化流動温度と安定なガラス構造の両立が可能となる。
Moreover, it is preferable that oxide glass contains V, Te, and Ag in total 80 mol% or more in conversion of an oxide. That is, it is preferable to satisfy V 2 O 5 + TeO 2 + Ag 2 O ≧ 80 mol%. By satisfying this relationship, it is possible to achieve both a low glass transition temperature, a softening flow temperature, and a stable glass structure.
酸化物ガラス中のＶ２Ｏ５の含有量は１０モル％以上３０モル％以下、ＴｅＯ２の含有量は３０モル％以上５０モル％以下、Ａｇ２Ｏの含有量は２０モル％以上４０モル％以下であることが好ましい。
The content of V 2 O 5 in the oxide glass is 10 mol% or more and 30 mol% or less, the content of TeO 2 is 30 mol% or more and 50 mol% or less, and the content of Ag 2 O is 20 mol% or more and 40 mol%. % Or less is preferable.
酸化物ガラスは、さらにＢａ、Ｐ、Ｗ、Ｌａ、アルカリ金属の少なくとも一種類の元素を含んでいてもよい。酸化物ガラスは結晶化後の物質や変化後の物質の融点が高ければ、接合の耐熱性が向上する。一方で、結晶化後の物資や変化後の物質が脆く、接合強度を低下させるような場合も生じる。このような場合に、これらの成分を含有させることにより、ガラス構造がより安定化し、接合強度の低下を抑制することができる。
The oxide glass may further contain at least one element of Ba, P, W, La, and alkali metal. When the oxide glass has a high melting point of the material after crystallization or the material after change, the heat resistance of bonding is improved. On the other hand, the material after crystallization or the material after change may be brittle and may reduce the bonding strength. In such a case, by containing these components, the glass structure is further stabilized, and a decrease in bonding strength can be suppressed.
酸化物ガラスは、ガラス転移温度が２００℃以下であることが好ましい。ガラス転移温度が２００℃以下のガラスを用いることにより、はんだ材と同程度の温度で接合することが可能となる。
The oxide glass preferably has a glass transition temperature of 200 ° C. or lower. By using glass having a glass transition temperature of 200 ° C. or lower, bonding can be performed at a temperature similar to that of the solder material.
添加材は、Ｓｉ粉末又は窒化ケイ素粉末である。これらは単独で用いても良いし、複数用いても良い。Ｓｉ粉末又は窒化ケイ素粉末は、接合時に、自然酸化膜を形成する金属、半金属及び半導体に形成された自然酸化膜及びその下層と反応し、冷却時に接合界面の再構成を促す。その結果、高い接合強度を得ることができる。
The additive is Si powder or silicon nitride powder. These may be used alone or in combination. The Si powder or silicon nitride powder reacts with the natural oxide film formed on the metal, metalloid and semiconductor forming the natural oxide film and its lower layer at the time of bonding, and promotes reconfiguration of the bonding interface at the time of cooling. As a result, high bonding strength can be obtained.
コージェライト、シリカ、ジルコン、ホルステライト、ムライト、β‐ユークリプトライト、β‐スポジューメン等のフィラーやＳｉＣ等を添加材として用いても、基材に形成された自然酸化膜及び／又はその下層と反応しないため、高い接合強度を得ることはできない。
Even if fillers such as cordierite, silica, zircon, holsterite, mullite, β-eucryptolite, β-spodumene, and SiC are used as additives, natural oxide film formed on the substrate and / or its lower layer Since it does not react, high bonding strength cannot be obtained.
また、添加剤としてＳｉ粉末又は窒化ケイ素粉末を用いると、Ａｇ粒子等の金属粒子を添加材として用いた場合よりも高い接合強度を得ることができる。Ａｇ粒子等の金属粒子は、熱膨張係数が大きく、熱処理及び冷却時におけるガラスの熱膨張を緩和できず、応力緩和が困難であるためである。
Further, when Si powder or silicon nitride powder is used as an additive, higher bonding strength can be obtained than when metal particles such as Ag particles are used as an additive. This is because metal particles such as Ag particles have a large coefficient of thermal expansion, cannot relax the thermal expansion of glass during heat treatment and cooling, and are difficult to relieve stress.
基材と、接合材の熱膨張係数が大きい場合、基材と接合材の界面で熱応力が生じ、高い接合強度が得られないことがある。Ｓｉ粉末又は窒化ケイ素粉末は、Ｖ及びＴｅを含む酸化物ガラスよりも熱膨張係数が低いため、接合材と基材の熱膨張係数の差を低減することができる。熱膨張の低減効果は添加する添加材の粒子径にも依存するため、添加材の粒子径は１００ｎｍ以上１００μｍ以下が好ましい。添加材の粒子径を１００ｎｍ以上とすることにより、添加材による熱膨張緩和の効果を向上できる。また添加材の粒子径を１００μｍ以下とすることにより、添加材の反応表面積を稼ぐことができ、基材との反応性を保つことができる。
When the thermal expansion coefficient of the base material and the bonding material is large, thermal stress is generated at the interface between the base material and the bonding material, and high bonding strength may not be obtained. Since the Si powder or the silicon nitride powder has a lower thermal expansion coefficient than the oxide glass containing V and Te, the difference in the thermal expansion coefficient between the bonding material and the base material can be reduced. Since the effect of reducing thermal expansion depends on the particle diameter of the additive to be added, the particle diameter of the additive is preferably 100 nm or more and 100 μm or less. By making the particle diameter of the additive 100 nm or more, the effect of relaxation of thermal expansion by the additive can be improved. Moreover, the reaction surface area of an additive can be earned by making the particle diameter of an additive into 100 micrometers or less, and the reactivity with a base material can be maintained.
酸化物ガラスと添加材の合計体積に対する酸化物ガラスの含有量は２０体積％超８０体積％未満であることが好ましく、３０体積％以上７０体積％以下であることがより好ましく、４０体積％以上６０体積％以下であることがさらに好ましい。ガラス組成物を２０体積％より多く含むことにより、接合時の流動性を保つことができ、密着性を向上することができる。その結果、高い接合強度を得ることができる。また、酸化物ガラスの含有量を８０体積％未満とすることにより、添加材の添加効果を向上することができる。
The content of the oxide glass with respect to the total volume of the oxide glass and the additive is preferably more than 20% by volume and less than 80% by volume, more preferably 30% by volume or more and 70% by volume or less, and 40% by volume or more. More preferably, it is 60 volume% or less. By containing more than 20 volume% of a glass composition, the fluidity | liquidity at the time of joining can be maintained and adhesiveness can be improved. As a result, high bonding strength can be obtained. Moreover, the addition effect of an additive can be improved by making content of oxide glass less than 80 volume%.
接合材には、Ｓｉ粉末又は窒化ケイ素粉末以外の添加材をさらに添加しても良い。添加材の種類によって接合時に発生する酸素、窒素を含むガス量が異なる。接合する基材の種類によって添加材を使い分けることで、さらに高い接合強度を得ることができる。
An additive other than Si powder or silicon nitride powder may be further added to the bonding material. The amount of gas containing oxygen and nitrogen generated during bonding varies depending on the type of additive. By using different additives depending on the types of base materials to be joined, higher joint strength can be obtained.
＜接合方法＞
上記の接合材を用いて基材を接合する方法としては、例えば以下の２つの方法があげられる。 <Join method>
Examples of the method of bonding the base material using the bonding material include the following two methods.
上記の接合材を用いて基材を接合する方法としては、例えば以下の２つの方法があげられる。 <Join method>
Examples of the method of bonding the base material using the bonding material include the following two methods.
Ｖ及びＴｅを含むガラス組成物と、添加材と、を含む接合材に、適宜溶媒を加えてペースト化したものを、基材に塗布して加熱することによって基材同士を接合する。ペースト化の際に用いる溶媒としては、例えば、水、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、メタノール、エタノール、プロパノール、エチレングリコール、グリセリン、ジメチルスルホキシド、テトラヒドロフラン、テルピネオール、ブチルヒドロキシアニソールなどが挙げられる。ペーストにはある程度の粘度が必要なため、テルピネオールやブチルヒドロキシアニソールが特に好ましい。これらの溶媒は単独で用いても良いし、複数混合しても良い。
The base materials are joined to each other by applying a paste prepared by adding a solvent to a joining material containing a glass composition containing V and Te and an additive, and heating the paste. Examples of the solvent used for pasting include water, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, methanol, ethanol, propanol, ethylene glycol, glycerin, dimethyl sulfoxide, tetrahydrofuran, and terpineol. And butylhydroxyanisole. Since the paste needs a certain viscosity, terpineol and butylhydroxyanisole are particularly preferable. These solvents may be used alone or in combination.
また、Ｖ及びＴｅを含むガラス組成物と、添加材と、を含む接合材に、さらにポリフッ化ビニリデン（ＰＶｄＦ）のような高分子系の添加材を加えて、シート化する。シート化された接合材を基材間に挟みこみ、加熱することにより接合する。ＰＶｄＦのような高分子系の添加材としては、例えば、アクリル系樹脂、ウレタン系樹脂、フェノール系樹脂、イミド系樹脂、グリオキザール系樹脂、ブタジエン系樹脂、メタクリル樹脂、フッ素系樹脂、スチレン系樹脂、エチレン系樹脂などが挙げられる。これらの樹脂は単独で用いても良いし、複数混合しても良い。このような高分子を混合した場合、基材の熱膨張係数差による応力の影響を緩和でき、接合強度の低下を抑制することができる。
Further, a polymer additive such as polyvinylidene fluoride (PVdF) is further added to a bonding material including a glass composition containing V and Te and an additive, thereby forming a sheet. The joining material formed into a sheet is sandwiched between base materials and joined by heating. Examples of polymeric additives such as PVdF include acrylic resins, urethane resins, phenolic resins, imide resins, glyoxal resins, butadiene resins, methacrylic resins, fluorine resins, styrene resins, Examples thereof include ethylene resins. These resins may be used alone or in combination. When such a polymer is mixed, the influence of stress due to the difference in thermal expansion coefficient of the base material can be alleviated, and a decrease in bonding strength can be suppressed.
ガラス組成物と添加材に高分子系添加剤を添加し、柔軟性の高いシート状に成形してから接合する場合は、ガラス組成物と添加材の合計体積％に対して、高分子系添加剤の添加量が５体積％以上７０体積％以下であることが好ましい。高分子系添加剤の体積％を５体積％以上とすることにより、高分子由来の柔軟性を活かし、シート状に成形することが容易となる。高分子系添加剤の体積を７０体積％以下とすることにより、ガラス組成物と添加材の効果低下を抑制でき、高い接合強度得ることができる。
When a polymer additive is added to the glass composition and the additive, and then formed into a highly flexible sheet, the polymer is added to the total volume% of the glass composition and the additive. The addition amount of the agent is preferably 5% by volume or more and 70% by volume or less. By setting the volume% of the polymer-based additive to 5% by volume or more, it becomes easy to form a sheet using the flexibility derived from the polymer. By setting the volume of the polymer-based additive to 70% by volume or less, it is possible to suppress a decrease in the effects of the glass composition and the additive and to obtain a high bonding strength.
接合時における雰囲気は、大気、または酸素ガス、または窒素ガスやアルゴンガスなどのも不活性雰囲気、水素ガス還元雰囲気などが挙げられ、いずれの場合も高い接合強度が得られる。接合時の雰囲気は、接合される基材の種類や用途によって使い分けることが好ましい。
The atmosphere at the time of bonding includes air, oxygen gas, nitrogen gas, argon gas, etc., inert atmosphere, hydrogen gas reducing atmosphere, etc. In any case, high bonding strength can be obtained. It is preferable that the atmosphere at the time of joining is properly used depending on the type and use of the substrates to be joined.
接合時の加熱方法は、恒温槽内での加熱が一般的である。レーザを透過する基材を用いた場合は、レーザ照射により光エネルギーを熱エネルギーに変換することで加熱し、接合することができる。
¡The heating method at the time of joining is generally heating in a thermostatic chamber. In the case of using a base material that transmits laser, heating can be performed by converting light energy into heat energy by laser irradiation.
上記接合材は、加熱することにより酸化物ガラスを軟化流動させることにより接合するよりも、一度、酸化物ガラスの結晶化温度以上に加熱し、酸化物ガラスを結晶化させてから、融解させることにより接合することが好ましい。これは、融解させることによりガラスの軟化流動よりも高い流動性を得ることで、接合界面へのガラス及び添加材の接触性及び密着性を向上させより高い反応性を得るためである。ただし、ガラスを結晶化し、融解せずとも、ガラスが高い軟化流動性を有した場合は結晶化する必要はない。
Rather than joining the bonding material by softening and flowing the oxide glass by heating, the bonding material is heated to a temperature equal to or higher than the crystallization temperature of the oxide glass to crystallize the oxide glass and then melt. It is preferable to join by. This is because by obtaining a higher fluidity than the softening flow of the glass by melting, the contactability and adhesion of the glass and additive to the bonding interface are improved and higher reactivity is obtained. However, it is not necessary to crystallize the glass if it has high softening fluidity without crystallizing and melting the glass.
接合時の加熱温度は、結晶化させた酸化物ガラスが融解する温度程度であることが好ましい。接合材にＶ、Ｔｅ、Ａｇを含む酸化物ガラスを用いた場合は、加熱温度は３２０～４２０℃であることが好ましい。
The heating temperature at the time of joining is preferably about the temperature at which the crystallized oxide glass melts. When an oxide glass containing V, Te, and Ag is used as the bonding material, the heating temperature is preferably 320 to 420 ° C.
接合時には荷重をかけることが好ましい。荷重をかけることにより接合層と基材の密着性が上がり、接合強度を向上させることができる。一方で、加圧しすぎると、接合層の接合材が加熱流動した際、基材間の端部から流出する虞がある。接合材が基材間の端部から流出すると、接合材が過少になり接合強度が低下する虞がある。したがって、接合時の荷重は０．０５ｋｇ／ｃｍ２以上、１．０ｋｇ／ｃｍ２以下であることが好ましい。
It is preferable to apply a load at the time of joining. By applying a load, the adhesion between the bonding layer and the base material can be increased, and the bonding strength can be improved. On the other hand, if the pressure is too high, the bonding material of the bonding layer may flow out from the end portion between the substrates when heated and flowed. When the bonding material flows out from the end portion between the base materials, the bonding material becomes too small and the bonding strength may be reduced. Therefore, the load during bonding is preferably 0.05 kg / cm 2 or more and 1.0 kg / cm 2 or less.
＜接合体＞
上記接合材料を用いて作製された接合体について説明する。図１に、本発明の一実施形態に係る接合体の構成を模式的に表す断面図を示す。接合体１は、自然酸化膜を形成する金属、半金属又は半導体からなる第一の基材１０１と、接合層１０２と、第二の基材１０３と、から構成される。 <Joint>
A bonded body manufactured using the bonding material will be described. In FIG. 1, sectional drawing which represents typically the structure of the conjugate | zygote which concerns on one Embodiment of this invention is shown. The joined body 1 includes afirst base material 101 made of a metal, a semimetal, or a semiconductor that forms a natural oxide film, a joining layer 102, and a second base material 103.
上記接合材料を用いて作製された接合体について説明する。図１に、本発明の一実施形態に係る接合体の構成を模式的に表す断面図を示す。接合体１は、自然酸化膜を形成する金属、半金属又は半導体からなる第一の基材１０１と、接合層１０２と、第二の基材１０３と、から構成される。 <Joint>
A bonded body manufactured using the bonding material will be described. In FIG. 1, sectional drawing which represents typically the structure of the conjugate | zygote which concerns on one Embodiment of this invention is shown. The joined body 1 includes a
第一の基材は、自然酸化膜を形成する金属、半金属又は半導体であればよく、第一の基材には酸化膜層も含まれるものとする。自然酸化膜を形成する金属、半金属及び半導体とは、具体的には、Ｔｉ（チタン）、Ｍｎ（マンガン）、Ｆｅ（鉄）、Ｃｏ（コバルト）、Ｎｉ（ニッケル）、Ｃｕ（銅）、Ｚｎ（亜鉛）、Ｚｒ（ジルコニウム）Ｎｂ（ニオブ）、Ｍｏ（モリブデン）、Ｗ（タングステン）、Ａｇ（銀）、Ｓｉ（ケイ素）、Ａｌ（アルミニウム）、Ｂｉ（ビスマス）、Ｇｅ（ゲルマニウム）、Ｓｎ（錫）、Ｉｎ（インジウム）Ｐｔ（白金）、Ａｕ（金）、またはこれらを含む合金が挙げられる。
The first substrate may be a metal, a semimetal, or a semiconductor that forms a natural oxide film, and the first substrate includes an oxide film layer. Specifically, the metal, metalloid and semiconductor forming the natural oxide film are Ti (titanium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Zr (zirconium) Nb (niobium), Mo (molybdenum), W (tungsten), Ag (silver), Si (silicon), Al (aluminum), Bi (bismuth), Ge (germanium), Sn (Tin), In (indium) Pt (platinum), Au (gold), or an alloy containing these.
接合層１０２は、（バナジウム）及びＴｅ（テルル）を含む酸化物と、添加材と、を含み、添加材はＳｉ又は窒化ケイ素を含む。
The bonding layer 102 includes an oxide containing (vanadium) and Te (tellurium) and an additive, and the additive contains Si or silicon nitride.
接合層１０２において、Ｖ及びＴｅを含む酸化物１０５と、添加材（Ｓｉ又は窒化ケイ素）１０４とは、図２に示すように分散していることが好ましい。図２では、酸化物中に添加材が分散した形態を示したが、添加材中に酸化物が分散していても良い。酸化物と添加材とが分散した形態となっていることにより、接合強度の低下を抑制できる。
In the bonding layer 102, the oxide 105 containing V and Te and the additive (Si or silicon nitride) 104 are preferably dispersed as shown in FIG. Although FIG. 2 shows a form in which the additive is dispersed in the oxide, the oxide may be dispersed in the additive. Since the oxide and the additive are dispersed, a decrease in bonding strength can be suppressed.
Ｖ及びＴｅを含む酸化物と、添加材と、の合計体積に対するＶ及びＴｅを含む酸化物の割合は、２０体積％超８０体積％未満であることが好ましく、３０体積％以上７０体積％以下であることがより好ましく、４０体積％以上６０体積％以下であることがさらに好ましい。
The ratio of the oxide containing V and Te to the total volume of the oxide containing V and Te and the additive is preferably more than 20% by volume and less than 80% by volume, and is 30% by volume or more and 70% by volume or less. It is more preferable that it is 40 volume% or more and 60 volume% or less.
接合層１０２は、空隙を有することが好ましい。第一の基材１０１又は第二の基材１０３と接合層の熱膨張係数が大きく異なる場合には、熱サイクルなどにより剥離する虞がある。接合層１０２内に空隙を分散させることにより、熱応力が緩和して熱サイクルに対する耐性を高めることが可能である。
The bonding layer 102 preferably has voids. When the thermal expansion coefficients of the first base material 101 or the second base material 103 and the bonding layer are greatly different, there is a risk of peeling due to a thermal cycle or the like. By dispersing the voids in the bonding layer 102, it is possible to relax the thermal stress and increase the resistance to thermal cycling.
接合層における空隙の割合は、１０体積％以下が好ましい。空隙の割合を１０体積％以下とすることにより、基材と接合材の接触面積の低下による接合強度の低下を抑制できる。また、空隙の大きさは概ね１０ｎｍ以上１０μｍ以下が好ましい。空隙の大きさを１０ｎｍ以上とすることにより空隙による応力緩和の効果を十分に得ることができる。空隙の大きさを１０μｍ以下とすることにより接合材と基材の接触を阻害せずに、高い接合強度を得ることができる。
The proportion of voids in the bonding layer is preferably 10% by volume or less. By setting the ratio of the voids to 10% by volume or less, it is possible to suppress a decrease in bonding strength due to a decrease in the contact area between the base material and the bonding material. Further, the size of the gap is preferably approximately 10 nm to 10 μm. By setting the size of the gap to 10 nm or more, the effect of stress relaxation due to the gap can be sufficiently obtained. By setting the size of the gap to 10 μm or less, high bonding strength can be obtained without impeding contact between the bonding material and the substrate.
Ｖ及びＴｅを含む酸化物は非晶質相を有していても良い。なお、接合材には酸化物ガラスが用いられるが、接合体の接合層に含まれるＶ及びＴｅを含む酸化物はガラス状態を保つ必要はない。Ｖ及びＴｅを含む酸化物は、ガラス状態であっても良いし、結晶化していてもよい。また、基材や接合層内の添加材と反応し、他の物質に変化していても良い。
The oxide containing V and Te may have an amorphous phase. Note that although oxide glass is used as the bonding material, the oxide containing V and Te contained in the bonding layer of the bonded body does not need to maintain a glass state. The oxide containing V and Te may be in a glass state or may be crystallized. Moreover, it may react with the additive in a base material or a joining layer, and may change into another substance.
酸化物相は、Ｖ、Ｔｅの他にＡｇを含むことが好ましく、Ｖ、Ｔｅ、Ａｇを酸化物換算で合計８０モル％以上含むことがさらに好ましい。また、酸化物相は、Ｂａ（バリウム）、Ｗ（タングステン）、Ｌａ（ランタン）、Ｐ（リン）、アルカリ金属の少なくともいずれかを含むことが好ましい。酸化物相がこれらを含むことにより、接合強度の低下を抑制することができる。
The oxide phase preferably contains Ag in addition to V and Te, and more preferably contains V, Te and Ag in total 80 mol% or more in terms of oxide. The oxide phase preferably contains at least one of Ba (barium), W (tungsten), La (lanthanum), P (phosphorus), and an alkali metal. By including these in the oxide phase, it is possible to suppress a decrease in bonding strength.
第二の基材１０３の材質は、金属やガラス、セラミックスなど、特に限定されない。金属の例としては、例えば、Ｃｕ（銅）、Ｎｉ（ニッケル）、Ｃｏ（コバルト）、Ｆｅ（鉄）、Ａｌ（アルミ）などを含む基材、またはそれらの合金が挙げられる。ガラスの例としては、ホウ酸系ガラス、ケイ酸系ガラス、リン酸系ガラス、バナジウム系ガラスなどが挙げられる。また、セラミックスの例としては、酸化アルミニウム、窒化アルミニウム、窒化ケイ素、炭化ケイ素などが挙げられる。一般的に、金属、ガラス、セラミックス、及び半導体は熱膨張係数が異なるため、接合面は熱サイクルに弱くなる。しかしながら、本発明の一実施形態においては、接合材に含まれるＳｉや窒化ケイ素などにより接合時にガスが発生し、発生したガスにより接合層に空隙が形成される。その空隙によって、熱膨張係数の差に起因した大きな熱応力が緩和されるため、熱サイクルに強い接合体が得られる。
The material of the second base material 103 is not particularly limited, such as metal, glass, and ceramics. Examples of the metal include, for example, base materials containing Cu (copper), Ni (nickel), Co (cobalt), Fe (iron), Al (aluminum), and the like, or alloys thereof. Examples of the glass include boric acid glass, silicic acid glass, phosphoric acid glass, and vanadium glass. Examples of ceramics include aluminum oxide, aluminum nitride, silicon nitride, and silicon carbide. In general, since metal, glass, ceramics, and semiconductor have different coefficients of thermal expansion, the joint surface is vulnerable to thermal cycling. However, in one embodiment of the present invention, gas is generated at the time of bonding by Si, silicon nitride, or the like contained in the bonding material, and voids are formed in the bonding layer by the generated gas. Since the large thermal stress due to the difference in thermal expansion coefficient is relieved by the voids, a bonded body resistant to thermal cycling can be obtained.
また、窒化アルミニウムのような窒化物では表面を酸化させると高い接合強度が得られる場合がある。そのため、第二の基材１０３には酸化膜層を含むものとする。また、他の表面処理をした場合も、改質された表面層も基材に含まれるものとする。
Also, a nitride such as aluminum nitride may have a high bonding strength when its surface is oxidized. Therefore, the second base material 103 includes an oxide film layer. In addition, even when other surface treatment is performed, a modified surface layer is also included in the base material.
接合体の構造は目視で確認でき、接合層内および基材と接合層の接合界面の組成や構造は、オージェ電子分光法、Ｘ線光電子分光法、蛍光Ｘ線分析、Ｘ線回折分析及び電子顕微鏡観察によって確認することができる。
The structure of the bonded body can be confirmed visually, and the composition and structure of the bonding layer and the bonding interface between the base material and the bonding layer are Auger electron spectroscopy, X-ray photoelectron spectroscopy, fluorescent X-ray analysis, X-ray diffraction analysis, and electron This can be confirmed by microscopic observation.
本発明の実施例を示して具体的に説明するが、本発明の技術的範囲はこれらに限定されるものではない。
The present invention will be specifically described with reference to examples, but the technical scope of the present invention is not limited thereto.
＜ガラス組成物＞
接合材に用いるガラス組成物は以下のように作製した。出発原料を所定のモル比になるように秤量した。具体的には、Ｖ２Ｏ５を２０．５モル％、ＴｅＯ２を３９．５モル％、Ａｇ２Ｏを３２．５モル％、ＷＯ３を５．０モル％、Ｌａ２Ｏ３を２．５モル％とした。
これらの出発原料は、株式会社高純度化学研究所製の酸化物粉末（純度９９．９％以上）を用いた。出発原料を混合してるつぼへ入れた。色が目視で均一になるまで混合し、混合粉末が入ったるつぼをガラス溶融炉内に設置し、過熱、融解した。約１０℃／ｍｉｎ．の昇温速度で昇温し、設定温度７５０℃で融解しているガラスを撹拌しながら１時間保持した。その後、るつぼをガラス溶融炉から取り出し、あらかじめ１５０℃に加熱しておいたプレートへガラスを流し込み、冷却した。室温まで冷却したガラスを粗粉砕しガラス組成物の粉末を製造した。これをガラス組成物Ａとした。 <Glass composition>
The glass composition used for the bonding material was prepared as follows. The starting material was weighed to a predetermined molar ratio. Specifically, 20.5 mol% of V 2 O 5 , 39.5 mol% of TeO 2 , 32.5 mol% of Ag 2 O, 5.0 mol% of WO 3 , 2 of La 2 O 3 .5 mol%.
As these starting materials, oxide powder (purity: 99.9% or more) manufactured by Kojundo Chemical Laboratory Co., Ltd. was used. The starting materials were mixed and placed in a crucible. The mixture was mixed until the color was visually uniform, and the crucible containing the mixed powder was placed in a glass melting furnace, heated and melted. About 10 ° C./min. The glass was melted at a set temperature of 750 ° C. and held for 1 hour while stirring. Thereafter, the crucible was removed from the glass melting furnace, and the glass was poured into a plate that had been heated to 150 ° C. in advance, and cooled. The glass cooled to room temperature was coarsely pulverized to produce a glass composition powder. This was designated as Glass Composition A.
接合材に用いるガラス組成物は以下のように作製した。出発原料を所定のモル比になるように秤量した。具体的には、Ｖ２Ｏ５を２０．５モル％、ＴｅＯ２を３９．５モル％、Ａｇ２Ｏを３２．５モル％、ＷＯ３を５．０モル％、Ｌａ２Ｏ３を２．５モル％とした。
これらの出発原料は、株式会社高純度化学研究所製の酸化物粉末（純度９９．９％以上）を用いた。出発原料を混合してるつぼへ入れた。色が目視で均一になるまで混合し、混合粉末が入ったるつぼをガラス溶融炉内に設置し、過熱、融解した。約１０℃／ｍｉｎ．の昇温速度で昇温し、設定温度７５０℃で融解しているガラスを撹拌しながら１時間保持した。その後、るつぼをガラス溶融炉から取り出し、あらかじめ１５０℃に加熱しておいたプレートへガラスを流し込み、冷却した。室温まで冷却したガラスを粗粉砕しガラス組成物の粉末を製造した。これをガラス組成物Ａとした。 <Glass composition>
The glass composition used for the bonding material was prepared as follows. The starting material was weighed to a predetermined molar ratio. Specifically, 20.5 mol% of V 2 O 5 , 39.5 mol% of TeO 2 , 32.5 mol% of Ag 2 O, 5.0 mol% of WO 3 , 2 of La 2 O 3 .5 mol%.
As these starting materials, oxide powder (purity: 99.9% or more) manufactured by Kojundo Chemical Laboratory Co., Ltd. was used. The starting materials were mixed and placed in a crucible. The mixture was mixed until the color was visually uniform, and the crucible containing the mixed powder was placed in a glass melting furnace, heated and melted. About 10 ° C./min. The glass was melted at a set temperature of 750 ° C. and held for 1 hour while stirring. Thereafter, the crucible was removed from the glass melting furnace, and the glass was poured into a plate that had been heated to 150 ° C. in advance, and cooled. The glass cooled to room temperature was coarsely pulverized to produce a glass composition powder. This was designated as Glass Composition A.
＜接合材＞
ガラス組成物ＡとＳｉ粉末の体積比率が５０体積％になるように秤量し、目視で色が均一になるまでメノウ乳鉢中で混合し、接合材の混合粉末を得た。その後、１０ｍｍφのダイスに０．２ｇの接合材の混合粉末を入れ、１トンの荷重をかけ、１分間保持し、接合材のペレットを製造した。この接合材の熱的特性を示差熱分析計にて評価した。示差熱分析計は試料及び基準物質の温度を一定のプログラムによって変化させながら、その試料と基準物質との温度差を温度の関数として測定する方法である。図３に接合材の熱的特性評価結果を示す。１８９℃付近にガラス組成物に起因するガラス転移点の吸熱挙動が見られた。軟化点は明確には判明しなかったが、ガラス組成物の結晶化に起因する発熱挙動が３３０℃から見られ、３７７℃付近に結晶化したガラス組成物の融点に起因する鋭い吸熱挙動が確認された。 <Bonding material>
The glass composition A and Si powder were weighed so that the volume ratio was 50% by volume, and mixed in an agate mortar until the color became uniform visually to obtain a mixed powder of the bonding material. Thereafter, 0.2 g of the mixed powder of the bonding material was put into a 10 mmφ die, a load of 1 ton was applied, and the mixture was held for 1 minute to produce a bonding material pellet. The thermal characteristics of this bonding material were evaluated with a differential thermal analyzer. The differential thermal analyzer is a method of measuring the temperature difference between the sample and the reference material as a function of temperature while changing the temperature of the sample and the reference material according to a certain program. FIG. 3 shows the thermal property evaluation results of the bonding material. The endothermic behavior of the glass transition point due to the glass composition was observed near 189 ° C. Although the softening point was not clearly clarified, an exothermic behavior due to crystallization of the glass composition was observed from 330 ° C., and a sharp endothermic behavior due to the melting point of the glass composition crystallized around 377 ° C. was confirmed. It was done.
ガラス組成物ＡとＳｉ粉末の体積比率が５０体積％になるように秤量し、目視で色が均一になるまでメノウ乳鉢中で混合し、接合材の混合粉末を得た。その後、１０ｍｍφのダイスに０．２ｇの接合材の混合粉末を入れ、１トンの荷重をかけ、１分間保持し、接合材のペレットを製造した。この接合材の熱的特性を示差熱分析計にて評価した。示差熱分析計は試料及び基準物質の温度を一定のプログラムによって変化させながら、その試料と基準物質との温度差を温度の関数として測定する方法である。図３に接合材の熱的特性評価結果を示す。１８９℃付近にガラス組成物に起因するガラス転移点の吸熱挙動が見られた。軟化点は明確には判明しなかったが、ガラス組成物の結晶化に起因する発熱挙動が３３０℃から見られ、３７７℃付近に結晶化したガラス組成物の融点に起因する鋭い吸熱挙動が確認された。 <Bonding material>
The glass composition A and Si powder were weighed so that the volume ratio was 50% by volume, and mixed in an agate mortar until the color became uniform visually to obtain a mixed powder of the bonding material. Thereafter, 0.2 g of the mixed powder of the bonding material was put into a 10 mmφ die, a load of 1 ton was applied, and the mixture was held for 1 minute to produce a bonding material pellet. The thermal characteristics of this bonding material were evaluated with a differential thermal analyzer. The differential thermal analyzer is a method of measuring the temperature difference between the sample and the reference material as a function of temperature while changing the temperature of the sample and the reference material according to a certain program. FIG. 3 shows the thermal property evaluation results of the bonding material. The endothermic behavior of the glass transition point due to the glass composition was observed near 189 ° C. Although the softening point was not clearly clarified, an exothermic behavior due to crystallization of the glass composition was observed from 330 ° C., and a sharp endothermic behavior due to the melting point of the glass composition crystallized around 377 ° C. was confirmed. It was done.
＜接合体＞
基材には１０ｍｍ角のＳｉ基板と酸化アルミニウムの基板を用いた。はじめに酸化アルミニウムの基板上へ接合材ペレットを設置し、そのペレットを挟むようにＳｉ基板を上に設置し、接合体の前駆体を得た。次に、その接合体の前駆体に荷重０．２５ｋｇ／ｃｍ２となるようにＳＵＳ製の重しを設置し、電気炉内へ投入した。その後、１０℃／ｍｉｎの昇温速度で４００℃まで昇温し、３０分保持し、室温まで自然冷却し、電気炉から取り出すことで接合体を製造した。この接合体の接着強度を接着面に平行なせん断荷重をＳｉチップにかけて測定した。また、剥離したＳｉ基板表面及び接合材の剥離面の結晶構造をＸ線回折測定により評価した。Ｘ線回折測定は、測定範囲：２θ＝１０～８０°、測定幅：０．０２°、管電圧：４８ｋＶ、管電流：２５ｍＡとし、回折ピーク位置を正確に測定するため、測定幅ごとに１秒ずつ固定することにより実施した。図４に剥離したＳｉ基板表面のＸ線回折結果、図５に接合材の剥離面のＸ線回折結果をそれぞれ示す。図４から、接合材中のＳｉ粉末に由来するピーク、Ｓｉ基板の（１００）配向面に由来するピークおよびガラス組成物から析出したＡｇに由来するピークが確認された。また、図５から、酸化アルミニウム基板に由来するピーク、ガラス組成物から析出したＡｇに由来するピーク、及び添加材であるＳｉ粉末のピークが確認された。これらの結果から、接合後の剥離界面では明確な異相は形成されていないことがわかった。 <Joint>
As the base material, a 10 mm square Si substrate and an aluminum oxide substrate were used. First, a bonding material pellet was placed on an aluminum oxide substrate, and a Si substrate was placed on top so as to sandwich the pellet to obtain a precursor of a joined body. Next, a weight made of SUS was placed on the precursor of the joined body so that the load would be 0.25 kg / cm 2, and it was put into an electric furnace. Then, it heated up to 400 degreeC with the temperature increase rate of 10 degree-C / min, hold | maintained for 30 minutes, naturally cooled to room temperature, and manufactured the conjugate | zygote by taking out from an electric furnace. The bonding strength of this bonded body was measured by applying a shear load parallel to the bonding surface to the Si chip. Moreover, the crystal structure of the peeled Si substrate surface and the peeled surface of the bonding material was evaluated by X-ray diffraction measurement. X-ray diffraction measurement has a measurement range of 2θ = 10 to 80 °, a measurement width of 0.02 °, a tube voltage of 48 kV, a tube current of 25 mA, and 1 for each measurement width in order to accurately measure the diffraction peak position. It was carried out by fixing every second. FIG. 4 shows the X-ray diffraction results of the peeled Si substrate surface, and FIG. 5 shows the X-ray diffraction results of the peeled surface of the bonding material. From FIG. 4, a peak derived from the Si powder in the bonding material, a peak derived from the (100) orientation plane of the Si substrate, and a peak derived from Ag precipitated from the glass composition were confirmed. Moreover, from FIG. 5, the peak derived from the aluminum oxide substrate, the peak derived from Ag deposited from the glass composition, and the peak of the Si powder as the additive were confirmed. From these results, it was found that no distinct heterogeneous phase was formed at the peel interface after bonding.
基材には１０ｍｍ角のＳｉ基板と酸化アルミニウムの基板を用いた。はじめに酸化アルミニウムの基板上へ接合材ペレットを設置し、そのペレットを挟むようにＳｉ基板を上に設置し、接合体の前駆体を得た。次に、その接合体の前駆体に荷重０．２５ｋｇ／ｃｍ２となるようにＳＵＳ製の重しを設置し、電気炉内へ投入した。その後、１０℃／ｍｉｎの昇温速度で４００℃まで昇温し、３０分保持し、室温まで自然冷却し、電気炉から取り出すことで接合体を製造した。この接合体の接着強度を接着面に平行なせん断荷重をＳｉチップにかけて測定した。また、剥離したＳｉ基板表面及び接合材の剥離面の結晶構造をＸ線回折測定により評価した。Ｘ線回折測定は、測定範囲：２θ＝１０～８０°、測定幅：０．０２°、管電圧：４８ｋＶ、管電流：２５ｍＡとし、回折ピーク位置を正確に測定するため、測定幅ごとに１秒ずつ固定することにより実施した。図４に剥離したＳｉ基板表面のＸ線回折結果、図５に接合材の剥離面のＸ線回折結果をそれぞれ示す。図４から、接合材中のＳｉ粉末に由来するピーク、Ｓｉ基板の（１００）配向面に由来するピークおよびガラス組成物から析出したＡｇに由来するピークが確認された。また、図５から、酸化アルミニウム基板に由来するピーク、ガラス組成物から析出したＡｇに由来するピーク、及び添加材であるＳｉ粉末のピークが確認された。これらの結果から、接合後の剥離界面では明確な異相は形成されていないことがわかった。 <Joint>
As the base material, a 10 mm square Si substrate and an aluminum oxide substrate were used. First, a bonding material pellet was placed on an aluminum oxide substrate, and a Si substrate was placed on top so as to sandwich the pellet to obtain a precursor of a joined body. Next, a weight made of SUS was placed on the precursor of the joined body so that the load would be 0.25 kg / cm 2, and it was put into an electric furnace. Then, it heated up to 400 degreeC with the temperature increase rate of 10 degree-C / min, hold | maintained for 30 minutes, naturally cooled to room temperature, and manufactured the conjugate | zygote by taking out from an electric furnace. The bonding strength of this bonded body was measured by applying a shear load parallel to the bonding surface to the Si chip. Moreover, the crystal structure of the peeled Si substrate surface and the peeled surface of the bonding material was evaluated by X-ray diffraction measurement. X-ray diffraction measurement has a measurement range of 2θ = 10 to 80 °, a measurement width of 0.02 °, a tube voltage of 48 kV, a tube current of 25 mA, and 1 for each measurement width in order to accurately measure the diffraction peak position. It was carried out by fixing every second. FIG. 4 shows the X-ray diffraction results of the peeled Si substrate surface, and FIG. 5 shows the X-ray diffraction results of the peeled surface of the bonding material. From FIG. 4, a peak derived from the Si powder in the bonding material, a peak derived from the (100) orientation plane of the Si substrate, and a peak derived from Ag precipitated from the glass composition were confirmed. Moreover, from FIG. 5, the peak derived from the aluminum oxide substrate, the peak derived from Ag deposited from the glass composition, and the peak of the Si powder as the additive were confirmed. From these results, it was found that no distinct heterogeneous phase was formed at the peel interface after bonding.
接合材中のＳｉ粉末の含有量を２０体積％に変えたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。
A bonding material was produced in the same procedure as in Example 1 except that the content of Si powder in the bonding material was changed to 20% by volume, and a bonded body was manufactured using the bonding material.
接合材中のＳｉ粉末の含有量を３０体積％に変えたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。
A bonding material was produced in the same procedure as in Example 1 except that the content of Si powder in the bonding material was changed to 30% by volume, and a bonded body was manufactured using the bonding material.
接合材中のＳｉ粉末の含有量を４０体積％に変えたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。
A bonding material was produced in the same procedure as in Example 1 except that the content of Si powder in the bonding material was changed to 40% by volume, and a bonded body was manufactured using the bonding material.
接合材中のＳｉ粉末の含有量を６０体積％に変えたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。
A bonding material was produced in the same procedure as in Example 1 except that the content of Si powder in the bonding material was changed to 60% by volume, and a bonded body was manufactured using the bonding material.
接合材中のＳｉ粉末の含有量を７０体積％に変えたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。
A bonding material was produced in the same procedure as in Example 1 except that the content of Si powder in the bonding material was changed to 70% by volume, and a bonded body was manufactured using the bonding material.
接合材中のＳｉ粉末の含有量を８０体積％に変えたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。
A bonding material was produced in the same procedure as in Example 1 except that the content of Si powder in the bonding material was changed to 80% by volume, and a bonded body was manufactured using the bonding material.
接合材中のＳｉ粉末をＳｉ３Ｎ４粉末に変えたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。なお、使用したＳｉ３Ｎ４粉末の粒子径５０μｍ以下であった。
A bonding material was prepared in the same procedure as in Example 1 except that the Si powder in the bonding material was changed to Si 3 N 4 powder, and a bonded body was manufactured using the bonding material. In addition, the particle diameter of the used Si 3 N 4 powder was 50 μm or less.
接合材中のＳｉ３Ｎ４粉末の含有量を２０体積％に変えたことを除いて実施例８と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。
A bonding material was prepared in the same procedure as in Example 8 except that the content of Si 3 N 4 powder in the bonding material was changed to 20% by volume, and a bonded body was manufactured using the bonding material.
接合材中のＳｉ３Ｎ４粉末の含有量を３０体積％に変えたことを除いて実施例８と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。
A joining material was produced in the same procedure as in Example 8 except that the content of Si 3 N 4 powder in the joining material was changed to 30% by volume, and a joined body was produced using the joining material.
接合材中のＳｉ３Ｎ４粉末の含有量を４０体積％に変えたことを除いて実施例８と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。
A joining material was produced in the same procedure as in Example 8 except that the content of Si 3 N 4 powder in the joining material was changed to 40% by volume, and a joined body was produced using the joining material.
接合材中のＳｉ３Ｎ４粉末の含有量を６０体積％に変えたことを除いて実施例８と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。
A joining material was produced in the same procedure as in Example 8 except that the content of Si 3 N 4 powder in the joining material was changed to 60% by volume, and a joined body was produced using the joining material.
接合材中のＳｉ３Ｎ４粉末の含有量を７０体積％に変えたことを除いて実施例８と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。
A joining material was produced in the same procedure as in Example 8 except that the content of Si 3 N 4 powder in the joining material was changed to 70% by volume, and a joined body was produced using the joining material.
接合材中のＳｉ３Ｎ４粉末の含有量を８０体積％に変えたことを除いて実施例８と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。
A joining material was produced in the same procedure as in Example 8 except that the content of Si 3 N 4 powder in the joining material was changed to 80% by volume, and a joined body was produced using the joining material.
接合材中のガラス組成物Ａをガラス組成物Ｂに変えたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。ガラス組成物Ｂの組成は、Ｖ２Ｏ５を２０．０モル％、ＴｅＯ２を３７．５モル％、Ａｇ２Ｏを３５．０モル％、ＢａＯを５．０モル％、ＷＯ３を２．０モル％、Ｌａ２Ｏ３を０．５モル％とした。
A bonding material was prepared in the same procedure as in Example 1 except that the glass composition A in the bonding material was changed to the glass composition B, and a bonded body was manufactured using the bonding material. The composition of the glass composition B is as follows: V 2 O 5 20.0 mol%, TeO 2 37.5 mol%, Ag 2 O 35.0 mol%, BaO 5.0 mol%, WO 3 2 0.0 mol% and La 2 O 3 were 0.5 mol%.
接合材中のガラス組成物をガラス組成物Ｂに変えたことを除いて実施例８と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。
A bonding material was produced in the same procedure as in Example 8 except that the glass composition in the bonding material was changed to the glass composition B, and a bonded body was manufactured using the bonding material.
(比較例１)
接合材中にＳｉ粉末を添加しなかったことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。 (Comparative Example 1)
A joining material was produced in the same procedure as in Example 1 except that no Si powder was added to the joining material, and a joined body was produced using the joining material.
接合材中にＳｉ粉末を添加しなかったことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。 (Comparative Example 1)
A joining material was produced in the same procedure as in Example 1 except that no Si powder was added to the joining material, and a joined body was produced using the joining material.
（比較例２）
接合材としてガラス組成物及びＳｉ粉末添加せず、Ｓｎ粒子のみ用いたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。 (Comparative Example 2)
A joining material was produced in the same procedure as in Example 1 except that only Sn particles were used without adding a glass composition and Si powder as a joining material, and a joined body was produced using the joining material.
接合材としてガラス組成物及びＳｉ粉末添加せず、Ｓｎ粒子のみ用いたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。 (Comparative Example 2)
A joining material was produced in the same procedure as in Example 1 except that only Sn particles were used without adding a glass composition and Si powder as a joining material, and a joined body was produced using the joining material.
（比較例３）
接合材としてガラス組成物及びＳｉ粉末添加せず、Ｓｎ３．５質量％Ａｇ粒子のみを用いたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。 (Comparative Example 3)
A bonding material was prepared in the same procedure as in Example 1 except that only the Sn 3.5 mass% Ag particles were used without adding the glass composition and Si powder as the bonding material, and the bonded body was formed using the bonding material. Manufactured.
接合材としてガラス組成物及びＳｉ粉末添加せず、Ｓｎ３．５質量％Ａｇ粒子のみを用いたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。 (Comparative Example 3)
A bonding material was prepared in the same procedure as in Example 1 except that only the Sn 3.5 mass% Ag particles were used without adding the glass composition and Si powder as the bonding material, and the bonded body was formed using the bonding material. Manufactured.
（比較例４）
接合材としてガラス組成物及びＳｉ粉末添加せず、Ａｇ粒子のみを用いたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。 (Comparative Example 4)
A joining material was produced in the same procedure as in Example 1 except that only Ag particles were used without adding a glass composition and Si powder as a joining material, and a joined body was produced using the joining material.
接合材としてガラス組成物及びＳｉ粉末添加せず、Ａｇ粒子のみを用いたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。 (Comparative Example 4)
A joining material was produced in the same procedure as in Example 1 except that only Ag particles were used without adding a glass composition and Si powder as a joining material, and a joined body was produced using the joining material.
（比較例５）
接合材中のＳｉ粉末をＳｉＯ２粉末に変えたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。 (Comparative Example 5)
A joining material was produced in the same procedure as in Example 1 except that the Si powder in the joining material was changed to SiO 2 powder, and a joined body was produced using the joining material.
接合材中のＳｉ粉末をＳｉＯ２粉末に変えたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。 (Comparative Example 5)
A joining material was produced in the same procedure as in Example 1 except that the Si powder in the joining material was changed to SiO 2 powder, and a joined body was produced using the joining material.
（比較例６）
接合材中のＳｉ粉末をＡｇ粉末に変えたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。 (Comparative Example 6)
A bonding material was prepared in the same procedure as in Example 1 except that the Si powder in the bonding material was changed to Ag powder, and a bonded body was manufactured using the bonding material.
接合材中のＳｉ粉末をＡｇ粉末に変えたことを除いて実施例１と同様の手順で接合材を作製し、その接合材を用いて接合体を製造した。 (Comparative Example 6)
A bonding material was prepared in the same procedure as in Example 1 except that the Si powder in the bonding material was changed to Ag powder, and a bonded body was manufactured using the bonding material.
＜接合強度の評価＞
実施例１～１６、比較例１～６に係る接合体について、その接合強度を評価した。表１に実施例及び比較例の接合強度を示す。表１の接合強度は、実施例５の接合強度を１．０としたときの相対値とした。 <Evaluation of bonding strength>
The joint strengths of the joined bodies according to Examples 1 to 16 and Comparative Examples 1 to 6 were evaluated. Table 1 shows the bonding strengths of the examples and comparative examples. The bonding strengths in Table 1 were relative values when the bonding strength of Example 5 was 1.0.
実施例１～１６、比較例１～６に係る接合体について、その接合強度を評価した。表１に実施例及び比較例の接合強度を示す。表１の接合強度は、実施例５の接合強度を１．０としたときの相対値とした。 <Evaluation of bonding strength>
The joint strengths of the joined bodies according to Examples 1 to 16 and Comparative Examples 1 to 6 were evaluated. Table 1 shows the bonding strengths of the examples and comparative examples. The bonding strengths in Table 1 were relative values when the bonding strength of Example 5 was 1.0.
表１より、一般的に接合材として用いられているＳｎ（比較例２）、Ｓｎ３．５質量％Ａｇ（比較例３）、及びＡｇ（比較例４）では、手で容易に剥離するほど接合強度が低かった。また、ガラス組成物単体を用いた比較例１、ガラス組成物とＳｉＯ２を含む接合材（比較例５）、ガラス組成物とＡｇ粒子を含む接合材（比較例６）でも同様の結果となった。一方で、ガラス組成物と、Ｓｉ粉末または窒化ケイ素粉末とを混合したものを接合材として用いた実施例１～１６は比較例１～６に比べ接合強度が向上していることが明らかとなった。
From Table 1, Sn (Comparative Example 2), Sn3.5 mass% Ag (Comparative Example 3), and Ag (Comparative Example 4), which are generally used as bonding materials, are bonded to each other as easily peeled by hand. The strength was low. Moreover, the same result was obtained in Comparative Example 1 using a glass composition alone, a bonding material containing the glass composition and SiO 2 (Comparative Example 5), and a bonding material containing the glass composition and Ag particles (Comparative Example 6). It was. On the other hand, it is clear that Examples 1 to 16 using a mixture of a glass composition and Si powder or silicon nitride powder as bonding materials have improved bonding strength compared to Comparative Examples 1 to 6. It was.
以上の結果から、Ｖ及びＴｅを含む酸化物ガラスと、Ｓｉ粉末又は窒化ケイ素粉末と、を含む接合材を用いることにより、自然酸化膜を形成する金属、半金属又は半導体からなる基材を、メタライズ処理無しに、はんだ材程度の低温で接合でき、高い接合強度が得られることが分かった。
From the above results, by using a bonding material containing oxide glass containing V and Te and Si powder or silicon nitride powder, a base material made of a metal, a semimetal or a semiconductor that forms a natural oxide film, It was found that, without metallization treatment, bonding can be performed at a temperature as low as the solder material, and high bonding strength can be obtained.
図６に接合材中の添加材の添加量と接合強度の関係を示す。添加材としてＳｉ粉末、窒化ケイ素粉末のいずれを用いた場合であっても、添加材をガラス組成物に対して２０体積％（実施例２、９）および８０体積％（実施例７、１４）添加した場合は、接合強度が低かった。一方で、添加材をガラス組成物に対して３０体積％～７０体積％添加した実施例１、３～６、８、１０～１３、１５、１６では、比較例で示される従来の接合材に比べ、著しく高い接合強度を示すことが明らかとなった。
Fig. 6 shows the relationship between the amount of additive added in the bonding material and the bonding strength. Regardless of whether Si powder or silicon nitride powder is used as the additive, the additive is 20% by volume (Examples 2 and 9) and 80% by volume (Examples 7 and 14) with respect to the glass composition. When added, the bonding strength was low. On the other hand, in Examples 1, 3 to 6, 8, 10 to 13, 15, and 16 in which the additive is added in an amount of 30 to 70% by volume with respect to the glass composition, the conventional bonding material shown in the comparative example In comparison, it was revealed that the bonding strength was extremely high.
１…接合体、１０１…第一の基材、１０２…接合層、１０３…第二の基材、１０４…添加材、１０５…Ｖ及びＴｅを含む酸化物
DESCRIPTION OF SYMBOLS 1 ... Bonded body, 101 ... 1st base material, 102 ... Joining layer, 103 ... 2nd base material, 104 ... Additive, 105 ... Oxide containing V and Te
Claims (15)
- Ｖ及びＴｅを含む酸化物ガラスと、添加材と、を含み、
前記添加材はＳｉ粉末又は窒化ケイ素粉末であることを特徴とする接合材。 An oxide glass containing V and Te, and an additive,
The joining material is characterized in that the additive is Si powder or silicon nitride powder. - 請求項１に記載の接合材であって、
前記酸化物ガラスと前記添加材の合計量に対する前記酸化物ガラスの含有量は２０体積％超８０体積％未満であることを特徴とする接合材。 The bonding material according to claim 1,
Content of the said oxide glass with respect to the total amount of the said oxide glass and the said additive is more than 20 volume% and less than 80 volume%, The joining material characterized by the above-mentioned. - 請求項１又は２に記載の接合材であって、
前記酸化物ガラスのガラス転移温度は２００℃以下であることを特徴とする接合材。 The bonding material according to claim 1 or 2,
The glass transition temperature of the oxide glass is 200 ° C. or less. - 請求項１乃至３のいずれか一項記載の接合材であって、
前記酸化物ガラスはＶ、Ｔｅ、Ａｇを酸化物換算で合計８０モル％以上含むことを特徴とする接合材。 The bonding material according to any one of claims 1 to 3,
The oxide glass contains a total of 80 mol% or more of V, Te, and Ag in terms of oxides. - 請求項４に記載の接合材であって、
前記酸化物ガラスは、さらにＢａ、Ｐ、Ｗ、Ｌａ、アルカリ金属の少なくとも一種類の元素を含むことを特徴とする接合材。 The bonding material according to claim 4,
The oxide glass further contains at least one element of Ba, P, W, La, and an alkali metal. - 請求項１乃至５のいずれか一項に記載の接合材は、自然酸化膜を形成する金属、半金属又は半導体からなる基材を接合することを特徴とする接合材。 The bonding material according to any one of claims 1 to 5, wherein a bonding material is formed by bonding a base material made of a metal, a semimetal, or a semiconductor that forms a natural oxide film.
- 第一の基材と、第二の基材と、前記第一の基材と前記第二の基材を接合する接合層と、を備える接合体であって、
前記第一の基材は自然酸化膜を形成する金属、半金属又は半導体のいずれかであって、
前記接合層は、Ｖ及びＴｅを含む酸化物と、添加材と、を含み、
前記添加材はＳｉ又は窒化ケイ素を含むことを特徴とする接合体。 A joined body comprising a first base material, a second base material, and a joining layer for joining the first base material and the second base material,
The first base material is any one of a metal, a semimetal, and a semiconductor that form a natural oxide film,
The bonding layer includes an oxide containing V and Te, and an additive.
The joined material, wherein the additive contains Si or silicon nitride. - 請求項７に記載の接合体であって、
前記酸化物は、非晶質相を有することを特徴とする接合体。 The joined body according to claim 7,
The joined body, wherein the oxide has an amorphous phase. - 請求項７又は８に記載の接合体であって、
前記接合層は、空隙を有することを特徴とする接合体。 The joined body according to claim 7 or 8,
The joined body is characterized in that the joining layer has voids. - 請求項７乃至９のいずれか一項に記載の接合体であって、
前記酸化物と、前記添加材の合計体積に対する前記酸化物の割合は２０体積％超８０体積％未満であることを特徴とする接合体。 A joined body according to any one of claims 7 to 9,
The joined body is characterized in that a ratio of the oxide to the total volume of the oxide and the additive is more than 20 volume% and less than 80 volume%. - 請求項７乃至１０いずれか一項に記載の接合体であって、
前記酸化物は、Ｖ、Ｔｅ、Ａｇを酸化物換算で合計８０モル％以上含むことを特徴とする接合体。 A joined body according to any one of claims 7 to 10,
The oxide contains V, Te, and Ag in total 80 mol% or more in terms of oxide. - 請求項１１に記載の接合体であって、
前記酸化物は、さらにＢａ、Ｐ、Ｗ、Ｌａ、アルカリ金属の少なくとも一種類の元素を含むことを特徴とする接合体。 The joined body according to claim 11,
The oxide further contains at least one element of Ba, P, W, La, and an alkali metal. - 請求項７乃至１２のいずれか一項に記載の接合体であって、
第一の基材はＳｉ、Ｔｉ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｚｒ、Ｎｂ、Ｍｏ、Ｗ、Ａｇ、Ａｌ、Ｂｉ、Ｇｅ、Ｓｎ、Ｉｎ、Ｐｔ、Ａｕのいずれかからなることを特徴とする接合体。 A joined body according to any one of claims 7 to 12,
The first substrate is made of any one of Si, Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, W, Ag, Al, Bi, Ge, Sn, In, Pt, and Au. A joined body characterized by that. - 請求項７乃至１２のいずれか一項に記載の接合体であって、
前記第二の基材がセラミックスであることを特徴とする接合体。 A joined body according to any one of claims 7 to 12,
The joined body, wherein the second base material is ceramics. - 請求項７乃至１２のいずれか一項に記載の接合体であって、
前記第二の基材が酸化アルミニウム、窒化アルミニウム、窒化ケイ素、炭化ケイ素のいずれかからなることを特徴とする接合体。 A joined body according to any one of claims 7 to 12,
The joined body, wherein the second substrate is made of any one of aluminum oxide, aluminum nitride, silicon nitride, and silicon carbide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-013781 | 2017-01-30 | ||
| JP2017013781A JP2020073418A (en) | 2017-01-30 | 2017-01-30 | Bonding material and bonded body |
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| WO2018139209A1 true WO2018139209A1 (en) | 2018-08-02 |
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Cited By (2)
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| WO2020263504A1 (en) * | 2019-06-24 | 2020-12-30 | Diebold Nixdorf International | Stripper assembly |
| US20230037628A1 (en) * | 2021-08-03 | 2023-02-09 | Lawrence Livermore National Security, Llc | Compliant suture-based joinery |
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| JPH06263478A (en) * | 1993-03-03 | 1994-09-20 | Iwaki Glass Kk | Lead-free low melting point glass |
| JPH08259262A (en) * | 1995-03-20 | 1996-10-08 | Nippon Electric Glass Co Ltd | Low melting point seal bonding composition |
| JP2005314136A (en) * | 2004-04-27 | 2005-11-10 | Matsushita Electric Ind Co Ltd | Sealing material for air tightly sealing and glass paste composition |
| JP2016050135A (en) * | 2014-08-29 | 2016-04-11 | 日立化成株式会社 | Lead-free low-melting point glass composition and low-temperature sealing glass frit, low-temperature sealing glass paste, conductive material and conductive glass paste containing the same, and glass-sealed component and electric and electronic component using them |
| JP2016050136A (en) * | 2014-08-29 | 2016-04-11 | 日立化成株式会社 | Lead-free low-melting point glass composition and low-temperature sealing glass frit, low-temperature sealing glass paste, conductive material and conductive glass paste containing the same, and glass-sealed component and electric and electronic component using them |
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- 2017-01-30 JP JP2017013781A patent/JP2020073418A/en active Pending
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| JPH06263478A (en) * | 1993-03-03 | 1994-09-20 | Iwaki Glass Kk | Lead-free low melting point glass |
| JPH08259262A (en) * | 1995-03-20 | 1996-10-08 | Nippon Electric Glass Co Ltd | Low melting point seal bonding composition |
| JP2005314136A (en) * | 2004-04-27 | 2005-11-10 | Matsushita Electric Ind Co Ltd | Sealing material for air tightly sealing and glass paste composition |
| JP2016050135A (en) * | 2014-08-29 | 2016-04-11 | 日立化成株式会社 | Lead-free low-melting point glass composition and low-temperature sealing glass frit, low-temperature sealing glass paste, conductive material and conductive glass paste containing the same, and glass-sealed component and electric and electronic component using them |
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| WO2020263504A1 (en) * | 2019-06-24 | 2020-12-30 | Diebold Nixdorf International | Stripper assembly |
| US20230037628A1 (en) * | 2021-08-03 | 2023-02-09 | Lawrence Livermore National Security, Llc | Compliant suture-based joinery |
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| JP2020073418A (en) | 2020-05-14 |
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