JPWO2017183687A1 - Lead-free low melting point composition, encapsulant, conductive material and electronic component - Google Patents
Lead-free low melting point composition, encapsulant, conductive material and electronic component Download PDFInfo
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- JPWO2017183687A1 JPWO2017183687A1 JP2018513211A JP2018513211A JPWO2017183687A1 JP WO2017183687 A1 JPWO2017183687 A1 JP WO2017183687A1 JP 2018513211 A JP2018513211 A JP 2018513211A JP 2018513211 A JP2018513211 A JP 2018513211A JP WO2017183687 A1 JPWO2017183687 A1 JP WO2017183687A1
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- 239000000203 mixture Substances 0.000 title claims abstract description 125
- 238000002844 melting Methods 0.000 title claims abstract description 59
- 230000008018 melting Effects 0.000 title claims abstract description 58
- 239000004020 conductor Substances 0.000 title claims description 17
- 239000008393 encapsulating agent Substances 0.000 title 1
- 125000004429 atom Chemical group 0.000 claims abstract description 80
- 239000002184 metal Substances 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 125000002346 iodo group Chemical group I* 0.000 claims abstract description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 10
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 229910052788 barium Inorganic materials 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 9
- 229910052738 indium Inorganic materials 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 8
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 7
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 7
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 6
- 239000003566 sealing material Substances 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 18
- 229910052714 tellurium Inorganic materials 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 229910052745 lead Inorganic materials 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 abstract description 26
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 238000007789 sealing Methods 0.000 description 24
- 239000011521 glass Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 16
- 229910000833 kovar Inorganic materials 0.000 description 15
- 150000001450 anions Chemical class 0.000 description 11
- 150000001768 cations Chemical class 0.000 description 10
- 239000000470 constituent Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 239000000945 filler Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910015363 Au—Sn Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- -1 silver halide Chemical class 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- BWVZAZPLUTUBKD-UHFFFAOYSA-N 3-(5,6,6-Trimethylbicyclo[2.2.1]hept-1-yl)cyclohexanol Chemical compound CC1(C)C(C)C2CC1CC2C1CCCC(O)C1 BWVZAZPLUTUBKD-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001374 Invar Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009429 electrical wiring Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000005394 sealing glass Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
- C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/253—Silica-free oxide glass compositions containing germanium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Glass Compositions (AREA)
- Photovoltaic Devices (AREA)
- Led Device Packages (AREA)
Abstract
低い温度領域での熱処理により金属表面又は金属表面と無機酸化物表面の双方を良好に封止できる無鉛低融点組成物が開示されている。当該組成物は,Mo及びPからなる群M1より選ばれる1種又は2種以上と,Mg,Ca,Sr,Ba,Y,ランタノイド,Ti,Zr,Nb,Ta,Mn,Fe,Co,Zn,B,Ga,In,Si,Ge,Sn,Bi,及びTeからなる群M2より選ばれる1種又は2種以上と,Ag,I,及びOを含み,(a)正のイオン価を有する全原子のモル数の和に対し,群M1に属する原子の総モル数の割合が5〜30%,Ag原子のモル数の割合が69〜92%,(群M2に属する原子の総モル数)/(群M1に属する原子の総モル数)が0.01〜0.7,(b)負のイオン価を有する原子の総モル数に対し,I原子のモル数の割合が15〜65%,O原子のモル数の割合が35〜85%,(c)負のイオン価を有する原子の総モル数に対しI及びOの各原子の総モル数の割合が少なくとも90%,(d)Pb原子,F原子及びCl原子の各含有量が何れも1000ppm未満である。 A lead-free low melting point composition that can satisfactorily seal a metal surface or both a metal surface and an inorganic oxide surface by heat treatment in a low temperature region is disclosed. The composition includes one or more selected from the group M1 consisting of Mo and P, and Mg, Ca, Sr, Ba, Y, lanthanoid, Ti, Zr, Nb, Ta, Mn, Fe, Co, Zn. , B, Ga, In, Si, Ge, Sn, Bi, and one or more selected from the group M2 consisting of Te, Ag, I, and O, and (a) having a positive ion valence The ratio of the total number of moles of atoms belonging to group M1 to the sum of the number of moles of all atoms is 5-30%, the ratio of moles of Ag atoms is 69-92%, (the total number of moles of atoms belonging to group M2 ) / (Total number of moles of atoms belonging to group M1) is 0.01 to 0.7, (b) the proportion of moles of I atoms is 15 to 65% of total moles of atoms having a negative ionic valence, O atoms The ratio of the number of moles of 35 to 85%, (c) the ratio of the total number of moles of each of the I and O atoms to the total number of moles of the negative ion valence is at least 90%, (d) Pb atoms, Each content of F atom and Cl atom is less than 1000 ppm.
Description
本発明は,無機組成物に関し,より具体的には無鉛低融点組成物,該組成物を含んでなる無鉛低融点封止材及び導電用材料,並びにこれらを用いた電子部品に関する。 The present invention relates to an inorganic composition, and more specifically, to a lead-free low melting point composition, a lead-free low melting point sealing material containing the composition, a conductive material, and an electronic component using these.
種々の無機低融点組成物が電気・電子機器業界において様々な用途で用いられている。例えば,水晶振動子,LED素子のような電気・電子部品の封止において,低融点(例えば,250℃)のAu−Sn合金はんだペーストや封止用ガラスフリットが,これをそれらの部品に塗布し焼成するという方法で用いられている。また,太陽電池パネルなどの電気電子部品には,パターニングされた電極および配線が形成されているが,配線の形成には金属粉末と低融点ガラス粉末とを混合した導電性ペースト等が用いられている。 Various inorganic low-melting-point compositions are used in various applications in the electric / electronic equipment industry. For example, in the sealing of electrical and electronic parts such as crystal resonators and LED elements, a low melting point (for example, 250 ° C.) Au—Sn alloy solder paste or sealing glass frit is applied to these parts. And then firing. In addition, patterned electrodes and wirings are formed on electrical and electronic parts such as solar cell panels. For the formation of wiring, conductive paste or the like in which metal powder and low-melting glass powder are mixed is used. Yes.
Au−Sn合金(特許文献1)は以前より用いられてきた材料であり信頼性はあるが,金を成分に含むため非常に高価である。 Au-Sn alloy (Patent Document 1) is a material that has been used for some time and is reliable, but it is very expensive because it contains gold as a component.
このため,封止材の調製に用いられる低融点ガラスとしては,より安価なPbO系ガラスやV2O5系ガラスも知られている。例えば,400℃未満の温度で封止可能なPbO系ガラス(特許文献2)や350℃以下で焼成可能なV2O5系ガラス(特許文献3)が知られている。For this reason, cheaper PbO glass and V 2 O 5 glass are also known as low melting point glass used for the preparation of the sealing material. For example, PbO-based glass (Patent Document 2) that can be sealed at a temperature lower than 400 ° C. and V 2 O 5 glass (Patent Document 3) that can be fired at 350 ° C. or lower are known.
他方,酸化銀及び/又はハロゲン化銀と他の金属酸化物(Pb,Vであってよい)を含んでなる,300〜330℃で使用できる封止材料が知られている(特許文献4)。 On the other hand, a sealing material that contains silver oxide and / or silver halide and another metal oxide (which may be Pb, V) and can be used at 300 to 330 ° C. is known (Patent Document 4). .
また,酸化銀,五酸化燐及びヨウ化銀を含んでなる封止材料も知られている(特許文献5,6)。 A sealing material containing silver oxide, phosphorus pentoxide and silver iodide is also known (Patent Documents 5 and 6).
このような状況において,近年,電気・電子材料の回路構成等の益々の微細化が進むのに伴い,より信頼性が高くかつ安価な封止材や低温での焼成が可能な導電性ペーストが求められるようになっているが,その要請には未だ十分に応えられていない。 Under these circumstances, as the circuit configuration of electrical and electronic materials has been increasingly miniaturized in recent years, more reliable and inexpensive sealing materials and conductive pastes that can be fired at low temperatures have been developed. Although it has been demanded, it has not yet been fully met.
本発明の一目的は,金属及び/又は無機酸化物からなる表面を有する封止対象に適用して,大気中で,350℃を超えない,好ましくは300℃を超えない低い温度領域において熱処理するとき,それらの表面に対し良好な濡れ性を示してよく拡がり,その後の冷却固化により当該表面に良好に接着(密着)した状態となることでこれを封止でき,また重ね合わせたそれら表面同士を接合もできる,無鉛の無機低融点組成物を提供することである。本発明の更なる一目的は,金属表面を選択的に封止するのに適した低融点組成物を提供することである。本発明の更なる一目的は,そのような組成物を含む低融点封止材や導電用材料を提供することである。本発明の尚も更なる一目的は,それらの封止材や導電用材料で封止,接合又は配線された電子部品を提供することである。 One object of the present invention is applied to a sealing object having a surface made of a metal and / or an inorganic oxide, and heat-treated in the air at a low temperature range not exceeding 350 ° C., preferably not exceeding 300 ° C. When they are spread well with good wettability to their surfaces, and then cooled and solidified, they can be sealed (adhered to) the surfaces, and can be sealed. It is an object of the present invention to provide a lead-free inorganic low-melting-point composition that can be bonded. It is a further object of the present invention to provide a low melting point composition suitable for selectively sealing a metal surface. A further object of the present invention is to provide a low-melting-point sealing material and a conductive material containing such a composition. A still further object of the present invention is to provide an electronic component sealed, bonded or wired with such a sealing material or conductive material.
本発明者は,Mo,及びPからなる群より選ばれる1種又は2種の構成要素と,Mg,Ca,Sr,Ba,Y,ランタノイド,Ti,Zr,Nb,Ta,Mn,Fe,Co,Zn,B,Ga,In,Si,Ge,Sn,Bi及びTeからなる群より選ばれる1種又は2種以上の構成要素と,更にAg,I及びOとを所定範囲内の割合で含んでなる組成物が,低い融点を有することを見出した。またそれらの低融点組成物が,大気中,上記の温度領域において良好なフロー性(流れて拡がり易いという性質)を示すこと,それらの組成物を無機酸化物表面や金属表面を有する封止対象に適用してそのような温度領域で熱処理して融解させた後,冷却させ固化させることで,それらの表面とよく密着した封止が可能であること,及び組成の調整により,金属表面に対する選択的な封止も可能であることを見出した。本発明は,これらの発見に更に検討を加えて完成するに至ったものである。すなわち,本発明は以下を提供する。 The inventor has one or two constituent elements selected from the group consisting of Mo and P, and Mg, Ca, Sr, Ba, Y, lanthanoid, Ti, Zr, Nb, Ta, Mn, Fe, and Co. , Zn, B, Ga, In, Si, Ge, Sn, Bi, and Te, one or more components selected from the group consisting of Te, and Ag, I, and O in a ratio within a predetermined range Was found to have a low melting point. In addition, these low-melting-point compositions exhibit good flowability (the property of being easy to flow and spread) in the above-mentioned temperature range in the atmosphere, and these compositions are sealed with an inorganic oxide surface or a metal surface. After being heat-treated and melted in such a temperature range, it can be cooled and solidified so that it can be sealed tightly to those surfaces, and the composition can be adjusted to select the metal surface. It has been found that a typical sealing is possible. The present invention has been completed by further studying these findings. That is, the present invention provides the following.
(1)Mo及びPからなる群M1より選ばれる1種又は2種の構成要素と,
Mg,Ca,Sr,Ba,Y,ランタノイド,Ti,Zr,Nb,Ta,Mn,Fe,Co,Zn,B,Ga,In,Si,Ge,Sn,Bi,及びTeからなる群M2より選ばれる1種又は2種以上の構成要素と,
構成要素Ag,I,及びOと
を含んでなる低融点組成物であって,
所定質量の該組成物中,
(a) 正のイオン価を有する全原子のモル数の和に対し,群M1に属する原子のモル数の合計の占める割合が5〜30%,Ag原子のモル数の占める割合が69〜92%であり,
(群M2に属する原子のモル数の合計)/(群M1に属する原子のモル数の合計)が0.01〜0.7であり,
(b) 負のイオン価を有する全原子のモル数の和に対し,I原子のモル数の占める割合が15〜65%,O原子のモル数の占める割合が35〜85%であり,
(c) 負のイオン価を有する全原子のモル数の和に対しI及びOの各原子のモル数の和の占める割合が少なくとも90%であり,そして
(d) Pb原子,F原子及びCl原子の各含有量が,何れも1000ppm未満である,
低融点組成物。
(2)Mo及びPからなる群M1より選ばれる1種又は2種の構成要素と,
Mg,Ca,Sr,Ba,Y,La,Ti,Zr,Nb,Ta,Mn,Fe,Co,Zn,B,In,Si,Ge,Sn,及びTeからなる群M3より選ばれる1種又は2種以上の構成要素と,
構成要素Ag,I,及びOと
を含んでなる低融点組成物であって,
所定質量の該組成物中,
(a) 正のイオン価を有する全原子のモル数の和に対し,群M1に属する原子のモル数の合計の占める割合が5〜30%,Ag原子のモル数の占める割合が69〜92%であり,
(群M3に属する原子のモル数の合計)/(群M1に属する原子のモル数の合計)が0.01〜0.7であり,
(b) 負のイオン価を有する全原子のモル数の和に対し,I原子のモル数の占める割合が15〜65%,O原子のモル数の占める割合が35〜85%であり,
(c) 負のイオン価を有する全原子のモル数の和に対しI及びOの各原子のモル数の和の占める割合が少なくとも90%であり,そして
(d) Pb原子,F原子及びCl原子の各含有量が,何れも1000ppm未満である,
低融点組成物。
(3)Mo及びPからなる群M1より選ばれる1種又は2種の構成要素と,
Ce,Ga及びBiからなる群M4より選ばれる1種又は2種以上の構成要素と,
構成要素Ag,I,及びOと
を含んでなる低融点組成物であって,
所定質量の該組成物中,
(a) 正のイオン価を有する全原子のモル数の和に対し,群M1に属する原子のモル数の合計の占める割合が5〜30%,Ag原子のモル数の占める割合が69〜92%であり,
(群M4に属する原子のモル数の合計)/(群M1に属する原子のモル数の合計)が0.01〜0.7であり,
(b) 負のイオン価を有する全原子のモル数の和に対し,I原子のモル数の占める割合が15〜65%,O原子のモル数の占める割合が35〜85%であり,
(c) 負のイオン価を有する全原子のモル数の和に対しBr,I,及びOの各原子のモル数の和の占める割合が少なくとも90%であり,そして
(d) Pb原子,F原子及びCl原子の各含有量が,何れも1000ppm未満である,
低融点組成物。
(4)Moを含有するものである,上記1〜3の何れかの低融点組成物。
(5)上記1〜4の何れかの低融点組成物を含んでなる低融点封止材。
(6)上記5の低融点封止材で封止された電子部品。
(7)上記6の低融点封止材を介して互いに接合されている2以上の部材を含んでなる,電子部品。
(8)水晶振動子,半導体素子,SAW素子又は有機EL素子である,上記7の電子部品。
(9)金属粉末と溶剤と上記1〜4の何れかの低融点組成物の粉末とを含んでなる導電用材料。
(10)上記9の導電用材料により形成された配線を含むものである電子部品。
(11)シリコン太陽電池又は圧電素子である,上記10の電子部品。(1) one or two components selected from the group M1 consisting of Mo and P;
Selected from the group M2 consisting of Mg, Ca, Sr, Ba, Y, lanthanoid, Ti, Zr, Nb, Ta, Mn, Fe, Co, Zn, B, Ga, In, Si, Ge, Sn, Bi, and Te One or more components to be
A low melting point composition comprising components Ag, I, and O,
In a predetermined mass of the composition;
(a) The ratio of the total number of moles of atoms belonging to the group M1 to the sum of the number of moles of all atoms having a positive ion valence is 5 to 30%, and the ratio of the number of moles of Ag atoms is 69 to 92 %,
(Total number of moles of atoms belonging to group M2) / (total number of moles of atoms belonging to group M1) is 0.01 to 0.7,
(b) The ratio of the number of moles of I atoms to the sum of the number of moles of all atoms having a negative ionic valence is 15 to 65%, and the ratio of the number of moles of O atoms is 35 to 85%.
(c) the proportion of the sum of the number of moles of each atom of I and O to the sum of the number of moles of all atoms having a negative ionic valence is at least 90%; and
(d) Each content of Pb atom, F atom and Cl atom is less than 1000 ppm,
Low melting point composition.
(2) one or two components selected from the group M1 consisting of Mo and P;
One selected from the group M3 consisting of Mg, Ca, Sr, Ba, Y, La, Ti, Zr, Nb, Ta, Mn, Fe, Co, Zn, B, In, Si, Ge, Sn, and Te, or Two or more components,
A low melting point composition comprising components Ag, I, and O,
In a predetermined mass of the composition;
(a) The ratio of the total number of moles of atoms belonging to the group M1 to the sum of the number of moles of all atoms having a positive ion valence is 5 to 30%, and the ratio of the number of moles of Ag atoms is 69 to 92 %,
(Total number of moles of atoms belonging to group M3) / (total number of moles of atoms belonging to group M1) is 0.01 to 0.7,
(b) The ratio of the number of moles of I atoms to the sum of the number of moles of all atoms having a negative ionic valence is 15 to 65%, and the ratio of the number of moles of O atoms is 35 to 85%.
(c) the proportion of the sum of the number of moles of each atom of I and O to the sum of the number of moles of all atoms having a negative ionic valence is at least 90%; and
(d) Each content of Pb atom, F atom and Cl atom is less than 1000 ppm,
Low melting point composition.
(3) one or two constituent elements selected from the group M1 consisting of Mo and P;
One or more components selected from the group M4 consisting of Ce, Ga and Bi;
A low melting point composition comprising components Ag, I, and O,
In a predetermined mass of the composition;
(a) The ratio of the total number of moles of atoms belonging to the group M1 to the sum of the number of moles of all atoms having a positive ion valence is 5 to 30%, and the ratio of the number of moles of Ag atoms is 69 to 92 %,
(Total number of moles of atoms belonging to group M4) / (total number of moles of atoms belonging to group M1) is 0.01 to 0.7,
(b) The ratio of the number of moles of I atoms to the sum of the number of moles of all atoms having a negative ionic valence is 15 to 65%, and the ratio of the number of moles of O atoms is 35 to 85%.
(c) the proportion of the sum of the number of moles of Br, I, and O atoms relative to the sum of the number of moles of all atoms having a negative ionic valence is at least 90%; and
(d) Each content of Pb atom, F atom and Cl atom is less than 1000 ppm,
Low melting point composition.
(4) The low melting point composition according to any one of the above 1 to 3, which contains Mo.
(5) A low melting point sealing material comprising the low melting point composition according to any one of the above 1 to 4.
(6) An electronic component sealed with the low-melting-point sealing material described in 5 above.
(7) An electronic component comprising two or more members joined to each other via the low melting point sealing material described in 6 above.
(8) The electronic component according to 7 above, which is a crystal resonator, a semiconductor element, a SAW element, or an organic EL element.
(9) A conductive material comprising a metal powder, a solvent, and a powder of any one of the low melting point compositions 1 to 4 above.
(10) An electronic component including a wiring formed of the conductive material described in 9 above.
(11) The electronic component as described above, which is a silicon solar cell or a piezoelectric element.
本発明の上記1の低融点組成物は,これを含んでなる低融点封止材を封止対象の無機酸化物及び/又金属からなる表面に適用し,大気中で350℃以下の幅広い温度領域において加熱融解させて適宜広げた後,冷却させ固化させることで,当該表面に対し密着性の良好な封止を達成できる。また,金属に対する融解時の濡れ性が特に高く,このため,無機酸化物表面を含む封止対象の封止に取り分け適している。また,金属表面への濡れ性が良いことから,金属粉末の焼結助剤として用いることもでき,そのことにより特に,低温焼成用の導電用材料や酸化物基板上への回路作成用の導電用材料の製造に適している。 In the low melting point composition of the present invention, the low melting point composition comprising the low melting point composition is applied to a surface made of an inorganic oxide and / or metal to be sealed, and has a wide temperature range of 350 ° C. or lower in the atmosphere. Sealing with good adhesion to the surface can be achieved by heating and melting in the region and spreading it appropriately, followed by cooling and solidification. In addition, the wettability with respect to metal is particularly high, which makes it particularly suitable for sealing a sealing target including an inorganic oxide surface. In addition, because it has good wettability to the metal surface, it can also be used as a sintering aid for metal powders, which makes it especially useful for conducting materials for low-temperature firing and for creating circuits on oxide substrates. Suitable for manufacturing materials.
本発明の上記2の低融点組成物も,これを含んでなる低融点封止材として,大気中で350℃を超えない幅広い温度領域において封止に使用することができる。当該封止材は,融解時において,無機酸化物に対するよりも金属に対して高い濡れ性を示す。このため,封止対象の金属表面同士のみを封止材で接合しようとする際,接合部の周囲に無機酸化物表面が存在しても,金属表面に適用された封止材が無機酸化物表面に流れて拡がるのを抑制でき,高い信頼性を以て金属表面に選択的な封止の実施を可能にする。 The low melting point composition of 2 of the present invention can also be used for sealing in a wide temperature range not exceeding 350 ° C. in the atmosphere as a low melting point sealing material containing the composition. The sealing material exhibits a higher wettability with respect to a metal than with an inorganic oxide during melting. For this reason, when trying to join only the metal surfaces to be sealed with a sealing material, even if an inorganic oxide surface exists around the joint, the sealing material applied to the metal surface is not an inorganic oxide. It can be prevented from flowing and spreading on the surface, and enables selective sealing on the metal surface with high reliability.
更に,本発明の組成物は,焼結助剤として金属粉末へ混合することで,低温での焼成が可能な導電用材料の提供を可能にする。 Furthermore, the composition of the present invention can provide a conductive material that can be fired at a low temperature by mixing into a metal powder as a sintering aid.
本発明の上記3の低融点組成物も,これを含んでなる低融点封止材として,大気中で350℃を超えない幅広い温度領域において封止に使用することができる。当該封止材は,融解時に無機酸化物表面と金属表面の両方に対する良好な濡れ性を示し,このため無機酸化物表面有する部材と金属表面を有する部材との封止による接合(異種材料接合)を高い信頼性を以て達成することを可能にする。 The low melting point composition of 3 of the present invention can also be used for sealing in a wide temperature range not exceeding 350 ° C. in the atmosphere as a low melting point sealing material containing the composition. The sealing material exhibits good wettability to both the inorganic oxide surface and the metal surface when melted. For this reason, bonding by sealing between a member having an inorganic oxide surface and a member having a metal surface (dissimilar material bonding) Can be achieved with high reliability.
本明細書において,「低融点」の語は,融点が350℃を超えないことを意味し,より好ましくは,融点が300℃を超えないことを意味する。本発明の組成物は,その融点に適した用途に使用できる。例えば,250〜300℃の融点を有する組成物は,Au−Sn合金封止材の安価な代替材料として用いることができる。また,融点が250℃を超えない組成物は,Au−Sn合金はんだが既に用いられている電子部品に更に封止を施す場合にも,好都合に使用できる。 In the present specification, the term “low melting point” means that the melting point does not exceed 350 ° C., more preferably, the melting point does not exceed 300 ° C. The composition of this invention can be used for the use suitable for the melting | fusing point. For example, a composition having a melting point of 250 to 300 ° C. can be used as an inexpensive alternative material for an Au—Sn alloy sealing material. In addition, a composition having a melting point not exceeding 250 ° C. can be advantageously used in the case of further sealing an electronic component for which an Au—Sn alloy solder has already been used.
本発明の組成物についてその構成要素の割合を規定するに際し,「所定質量」の該組成物というとき,「所定質量」の語は特定の固定された質量を意味せず,任意の質量であってよい。本発明は,特定の1種又は2種以上の原子について,当該原子と同じ符号のイオン価を有する全原子のモル数の和に対する当該特定の原子(1種又は2種以上)のモル数の割合(%)が求まればよいからである。 In defining the proportions of the components of the composition of the present invention, the term “predetermined mass” of the composition means that the term “predetermined mass” does not mean a specific fixed mass, but an arbitrary mass. It's okay. The present invention relates to the number of moles of the specific atom (one or more) with respect to the sum of the number of moles of all atoms having the same ionic valence as that atom. This is because the ratio (%) may be obtained.
本明細書において,正のイオン価を有する全原子のモル数の和に対する同符号のイオン価を有する特定の原子(1種又は2種以上)のモル数の占める割合を,便宜上それ(ら)特定の原子の「カチオン%」ともいう。負のイオン価を有する原子の場合,同様に「アニオン%」ともいう。 In the present specification, for the sake of convenience, the ratio of the number of moles of a specific atom (one or more) having the same sign ionic valence to the sum of the moles of all atoms having a positive ionic valence is It is also called “% cation” of a specific atom. In the case of an atom having a negative ionic valence, it is also referred to as “anion%”.
本発明の組成物は,
Mo及びPからなる群M1より選ばれる1種又は2種の構成要素と,
Mg,Ca,Sr,Ba,Y,ランタノイド,Ti,Zr,Nb,Ta,Mn,Fe,Co,Zn,B,Ga,In,Si,Ge,Sn,Bi及びTeからなる群M2より選ばれる1種又は2種以上の構成要素と,
構成要素Ag,I,及びOとを
含んでなる低融点組成物であって,
所定質量の該組成物中,
(a) 正のイオン価を有する全原子のモル数の和に対し群M1に属する原子のモル数の合計の占める割合が5〜30%であり,Ag原子のモル数の占める割合が69〜92%であり,
(群M2に属する原子のモル数の合計)/(群M1に属する原子のモル数の合計)が0.01〜0.7であり,
(b) 負のイオン価を有する全原子のモル数の和に対し,I原子のモル数の占める割合が15〜65%,及びO原子のモル数の占める割合が35〜85%であり,
(c) 負のイオン価を有する全原子のモル数の和に対しI,及びOの各原子のモル数の和の占める割合が少なくとも80%であり,そして
(d) Pb原子,F原子及びCl原子の各含有量が,何れも1000ppm未満である。The composition of the present invention comprises:
One or two components selected from the group M1 consisting of Mo and P;
Selected from the group M2 consisting of Mg, Ca, Sr, Ba, Y, lanthanoid, Ti, Zr, Nb, Ta, Mn, Fe, Co, Zn, B, Ga, In, Si, Ge, Sn, Bi, and Te One or more components, and
A low melting point composition comprising components Ag, I, and O,
In a predetermined mass of the composition;
(a) The ratio of the total number of moles of atoms belonging to the group M1 to the sum of the number of moles of all atoms having a positive ionic valence is 5 to 30%, and the ratio of moles of Ag atoms is 69 to 92%
(Total number of moles of atoms belonging to group M2) / (total number of moles of atoms belonging to group M1) is 0.01 to 0.7,
(b) The ratio of the number of moles of I atoms to the sum of the number of moles of all atoms having a negative ionic valence is 15 to 65%, and the ratio of the number of moles of O atoms is 35 to 85%,
(c) the proportion of the sum of the number of moles of each atom of I and O to the sum of the number of moles of all atoms having a negative ionic valence is at least 80%; and
(d) Each content of Pb atom, F atom and Cl atom is less than 1000 ppm.
当該組成物は,350℃を超えない,好ましくは300℃を超えない温度領域で良好なフロー性を有している。従って,当該組成物を,例えば粒子(例えば,粉末)の形で,封止対象の金属又は無機酸化物からなる表面に適用しそのような領域の温度に加熱することで,封止対象の表面に流れ拡がるから,これを冷却して固化させることにより,封止対象の表面に強く密着した状態となってこれを封止することができる。 The composition has good flowability in a temperature range not exceeding 350 ° C., preferably not exceeding 300 ° C. Therefore, by applying the composition to a surface made of a metal or inorganic oxide to be sealed, for example in the form of particles (eg powder) and heating to the temperature of such a region, the surface to be sealed Therefore, by cooling and solidifying it, it can be sealed tightly to the surface to be sealed.
Agは本発明の組成物の必須成分である。Agには組成物の液相線温度を低下させる効果やガラス相を形成させる効果がある。これらの効果の利用のため,Agの含有量は,好ましくは69〜92カチオン%,より好ましくは73〜89カチオン%,更に好ましくは75〜87カチオン%である。 Ag is an essential component of the composition of the present invention. Ag has the effect of lowering the liquidus temperature of the composition and the effect of forming a glass phase. In order to utilize these effects, the Ag content is preferably 69 to 92 cation%, more preferably 73 to 89 cation%, and still more preferably 75 to 87 cation%.
Mo及びPからなる群M1より選ばれる構成要素には,組成物の液相線温度を低下させる効果やガラス相を形成させる効果がある。これらの効果の利用のため群M1のうち1種又は2種を含有させる。群M1に属する構成要素の含有量は合計で,好ましくは5〜30カチオン%,より好ましくは8〜28カチオン%,更に好ましくは10〜25カチオン%である。 The component selected from the group M1 consisting of Mo and P has an effect of lowering the liquidus temperature of the composition and an effect of forming a glass phase. In order to use these effects, one or two of the groups M1 are contained. The total content of the constituent elements belonging to the group M1 is preferably 5 to 30 cation%, more preferably 8 to 28 cation%, and still more preferably 10 to 25 cation%.
耐水性の高い組成物を得るためには群M1の構成要素のうちとしてMoを含有させることが好ましく,Moのみを含有させることがより好ましい。 In order to obtain a composition having high water resistance, it is preferable to include Mo as a constituent element of the group M1, and it is more preferable to include only Mo.
Mg,Ca,Sr,Ba,Y,ランタノイド,Ti,Zr,Nb,Ta,Mn,Fe,Co,Zn,B,Ga,In,Si,Ge,Sn,Bi,及びTeからなる群M2より選ばれる構成要素は,本発明の組成物の接触角を変化させる効果,特に金属表面への接触角を小さくさせる(即ち,濡れ性を高める)効果がある。この効果の利用のため,群M2に属する構成要素のうち1種又は2種以上を含有させる。また,(群M2に属する原子のモル数の合計)/(群M1に属する原子のモル数の合計)は,好ましくは0.01〜0.7,より好ましくは0.02〜0.6,更に好ましくは0.03〜0.5である。 Selected from the group M2 consisting of Mg, Ca, Sr, Ba, Y, lanthanoid, Ti, Zr, Nb, Ta, Mn, Fe, Co, Zn, B, Ga, In, Si, Ge, Sn, Bi, and Te The component to be formed has an effect of changing the contact angle of the composition of the present invention, and in particular, an effect of reducing the contact angle to the metal surface (that is, improving wettability). In order to use this effect, one or more of the constituent elements belonging to the group M2 are contained. Further, (total number of moles of atoms belonging to group M2) / (total number of moles of atoms belonging to group M1) is preferably 0.01 to 0.7, more preferably 0.02 to 0.6, More preferably, it is 0.03-0.5.
群M2に属する構成要素のうち,Mg,Ca,Sr,Ba,Y,La,Ti,Zr,Nb,Ta,Mn,Fe,Co,Zn,B,In,Si,Ge,Sn,及びTeからなる群M3から選ばれる構成要素は,無機酸化物表面への接触角を低下させる効果が弱い。そのため,封止対象の表面の金属部分同士を接合させる場合において,接合部の周囲に無機酸化物表面が存在するときに無機酸化物表面に低融点組成物がフローすることを抑制したいなら,群M3に属する構成要素のうち1種又は2種以上を,群M2に属する他の構成要素(La以外のランタノイド,Ga,Bi)よりも優先して含有させることが好ましい。 Among the elements belonging to the group M2, Mg, Ca, Sr, Ba, Y, La, Ti, Zr, Nb, Ta, Mn, Fe, Co, Zn, B, In, Si, Ge, Sn, and Te The component selected from the group M3 is weak in reducing the contact angle with the inorganic oxide surface. Therefore, when joining metal parts on the surfaces to be sealed, if it is desired to suppress the low melting point composition from flowing to the inorganic oxide surface when the inorganic oxide surface is present around the joint, It is preferable to contain one or more of the constituent elements belonging to M3 in preference to other constituent elements belonging to the group M2 (lanthanoids other than La, Ga, Bi).
群M2のうち,Ce,Ga及びBiからなる群M4から選ばれる構成要素は,酸化物への接触角も低い。そのため,無機酸化物表面と金属表面とを接合させる場合においては群M4に属する構成要素のうち1種又は2種以上を,群M2に属する他の構成要素よりも優先して含有させることが好ましい。 Among the group M2, the component selected from the group M4 consisting of Ce, Ga and Bi has a low contact angle to the oxide. Therefore, in the case where the inorganic oxide surface and the metal surface are joined, it is preferable to contain one or more of the constituent elements belonging to the group M4 in preference to the other constituent elements belonging to the group M2. .
Iは本発明の組成物の必須成分である。Iは,組成物の液相線温度を低下させる効果やガラス相を形成させる効果がある。本発明の組成物におけるIの含有量は,好ましくは15〜65アニオン%,より好ましくは17〜60アニオン%,更に好ましくは20〜57アニオン%である。 I is an essential component of the composition of the present invention. I has the effect of lowering the liquidus temperature of the composition and the effect of forming a glass phase. The content of I in the composition of the present invention is preferably 15 to 65 anion%, more preferably 17 to 60 anion%, still more preferably 20 to 57 anion%.
Oは本発明の組成物の必須成分である。Oは組成物の耐水性及び無機酸化物表面や金属表面との密着性を飛躍的に高める効果がある。この効果を利用するには,Oの含有量は,好ましくは35〜85アニオン%,より好ましくは40〜83アニオン%,更に好ましくは43〜80アニオン%である。 O is an essential component of the composition of the present invention. O has the effect of dramatically improving the water resistance of the composition and the adhesion to the surface of the inorganic oxide or the metal. In order to utilize this effect, the content of O is preferably 35 to 85 anion%, more preferably 40 to 83 anion%, and still more preferably 43 to 80 anion%.
I及びOの含有量は合計で,好ましくは80アニオン%以上,より好ましくは90アニオン%以上,更に好ましくは99アニオン%以上である。 The total content of I and O is preferably 80 anion% or more, more preferably 90 anion% or more, and further preferably 99 anion% or more.
本発明の組成物は,Pbを実質的に含まない。Pbは環境に有害な成分である。ここに,Pbを「実質的に含まない」とは,不純物として微量が混入する場合でも,Pbの含有量が1000ppm未満であることをいう。Pbの含有量はより好ましくは100ppm未満である。 The composition of the present invention is substantially free of Pb. Pb is a component harmful to the environment. Here, “substantially does not contain” Pb means that the content of Pb is less than 1000 ppm even when a trace amount is mixed as an impurity. The content of Pb is more preferably less than 100 ppm.
本発明の組成物は,F及びClを実質的に含まない。これらの元素は,封止対象の表面が金属である場合にその腐食を招くおそれがある。ここに,F及びClを「実質的に含まない」とは,不純物としてそれらが微量に混入する場合でも,その含有量がそれぞれ1000ppm未満であることをいう。F及びClの含有量はより好ましくはそれぞれ100ppm未満である。 The composition of the present invention is substantially free of F and Cl. These elements may cause corrosion when the surface to be sealed is a metal. Here, “substantially does not contain” F and Cl means that the content is less than 1000 ppm, even if they are mixed in a trace amount as impurities. The contents of F and Cl are more preferably less than 100 ppm each.
Brは本発明の組成物の任意成分である。Brには,組成物の固相線温度を高め,更に無機酸化物に対する濡れ性を向上させる効果があり,そのため,組成物の耐熱温度を高めつつ比較的低い温度での封止を可能にする。また,Brは,ハロゲンの中では本発明の低融点組成物から揮発しにくい成分である。更にBrは,封止対象における金属材料の腐食を起こしにくい成分である。これらの効果との関係から,Brの含有量は好ましくは0〜10アニオン%である。 Br is an optional component of the composition of the present invention. Br has an effect of increasing the solidus temperature of the composition and further improving the wettability with respect to the inorganic oxide. Therefore, it enables sealing at a relatively low temperature while increasing the heat resistance temperature of the composition. . Further, Br is a component that hardly volatilizes from the low melting point composition of the present invention in halogen. Further, Br is a component that is unlikely to cause corrosion of the metal material in the object to be sealed. From the relationship with these effects, the content of Br is preferably 0 to 10 anion%.
本発明の組成物は,上記したAg,群M1及び群M2に属する以外の正のイオン価を有する原子を含んでもよい。それらの原子は,少量の含有であれば本発明の組成物の固相線温度及び液相線温度を低下させる効果が期待できるが,濡れ性を悪化させるおそれがある。このため,それらの合計含有量は,好ましくは14.5カチオン%以下,より好ましくは7カチオン%以下,更に好ましくは3カチオン%以下である。 The composition of the present invention may contain atoms having positive ionic valences other than those described above belonging to Ag, group M1, and group M2. If these atoms are contained in a small amount, the effect of lowering the solidus temperature and liquidus temperature of the composition of the present invention can be expected, but the wettability may be deteriorated. For this reason, the total content thereof is preferably 14.5 cation% or less, more preferably 7 cation% or less, and still more preferably 3 cation% or less.
本発明の組成物は,加熱し融解することで目的の低融点組成物を与えることになるように予め調合された各種原料試薬粉末の混合物の形で提供してもよい。また,そのような混合物を加熱し溶融した後に冷却することで得られる,固溶体や複ハロゲン化物,ガラス相が形成されている形態の材料とすることもできる。固溶体や複ハロゲン化物,ガラス相が形成されていると,より短時間の加熱で融解しやすい組成物となることから,そのような形態の組成物であることがより好ましい。また,本発明の組成物は,酸,塩基,又は塩を含んだ水溶液を反応させ沈殿させることによっても製造することができる。 The composition of the present invention may be provided in the form of a mixture of various raw material reagent powders prepared in advance so as to give the desired low melting point composition by heating and melting. Moreover, it can also be set as the material of the form in which the solid solution, the double halide, and the glass phase which are obtained by heating, melting, and cooling such a mixture are formed. When a solid solution, a double halide, or a glass phase is formed, it becomes a composition that is easily melted by heating in a shorter time, and thus a composition in such a form is more preferable. The composition of the present invention can also be produced by reacting and precipitating an aqueous solution containing an acid, base, or salt.
また,本発明の組成物は,粉末やビーズ,シート状,ロッド状等に加工して封止材として用いることができる。作業性の向上という点から水,有機溶剤,分散剤,増粘剤等と混合してペースト状の封止材としても用いることができる。有機溶剤としてはターピネオール,セロソルブ,イソボルニルシクロヘキサノール等を用いることができる。また,種々の特性の向上或いは性能付加の観点から,フィラーを含んだ形態のものとすることもできる。例えば,導電性の付与のためには,金属(例えば,金属銀等),カーボンナノチューブ等の導電性フィラーを含んだ形態のものとすることができ,熱伝導性の付与のためには,高い熱伝導性を有するフィラー(例えば,窒化アルミニウム,炭化ケイ素等)を含んだ形態のものとすることができ,熱膨張の抑制のためには,熱膨張率の小さいフィラー(例えば,ZrW2O8やインバー合金等)を含んだ形態のものとすることができ,また,脆性の改善のためには耐熱性のある有機高分子材料(例えば,ポリイミド,シリコーン,ポリテトラフルオロエチレン,ポリフェニレンスルファイド,フッ素ゴム等)を含んだ形態のものとすることができる。これらのフィラーは,本発明の組成物が用いられる封止対象の使用態様・使用環境に応じて求められる性能に合わせ,本発明の組成物の構成要素の一部をなすものとして配合すればよい。但し,それらフィラーは,封止のための加熱処理においても,更には封止後の封止対象(電子機器等)の使用環境においても,一貫して固体粒子であり,フィラー以外の部分の組成に影響を及ぼさないから,フィラーを構成する原子の正又は負のイオン価は,本発明の組成物の定義には関与しない。The composition of the present invention can be processed into powder, beads, sheets, rods, etc. and used as a sealing material. From the viewpoint of improving workability, it can be mixed with water, an organic solvent, a dispersant, a thickener and the like and used as a paste-like sealing material. As the organic solvent, terpineol, cellosolve, isobornylcyclohexanol and the like can be used. In addition, from the viewpoint of improving various characteristics or adding performance, a form including a filler can also be used. For example, in order to impart conductivity, it may be in a form containing a conductive filler such as a metal (for example, metallic silver) or carbon nanotube, and high in order to impart thermal conductivity. A filler having a thermal conductivity (for example, aluminum nitride, silicon carbide, etc.) can be used. In order to suppress thermal expansion, a filler having a low coefficient of thermal expansion (for example, ZrW 2 O 8 And invar alloys, etc., and in order to improve brittleness, heat resistant organic polymer materials (for example, polyimide, silicone, polytetrafluoroethylene, polyphenylene sulfide, (A fluororubber or the like). These fillers may be blended as part of the constituents of the composition of the present invention in accordance with the performance required according to the usage mode and environment of the sealing object in which the composition of the present invention is used. . However, these fillers are consistently solid particles both in the heat treatment for sealing and in the usage environment of the objects to be sealed (electronic devices, etc.) after sealing. Therefore, the positive or negative ionic valence of the atoms constituting the filler does not contribute to the definition of the composition of the present invention.
本発明の組成物を封止に用いる場合,封止対象は,その表面が,種々の金属,非金属(酸化物,フッ化物,窒化物,炭化物,有機ポリマー材料等)で構成されたものであることができる。本発明の組成物には,金属を濡らす性質があるため,封止対象の少なくとも一部が金属である場合に用いるのが特に好ましい。 When the composition of the present invention is used for sealing, the surface to be sealed is composed of various metals and nonmetals (oxides, fluorides, nitrides, carbides, organic polymer materials, etc.). Can be. Since the composition of the present invention has a property of wetting metal, it is particularly preferable to use it when at least a part of the object to be sealed is metal.
本発明の組成物は,封止対象の表面の材質及び封止の目的に応じて,以下のように選択することができる。 The composition of the present invention can be selected as follows according to the material of the surface to be sealed and the purpose of sealing.
(1)本発明の組成物を金属からなる表面に適用する場合:次の条件Aを満たす組成物であること。
条件A:250℃におけるコバール(Kovar)板への接触角が40°以下,又は300℃におけるコバール板への接触角が20°以下。(1) When the composition of the present invention is applied to a metal surface: the composition satisfies the following condition A.
Condition A: The contact angle to the Kovar plate at 250 ° C. is 40 ° or less, or the contact angle to the Kovar plate at 300 ° C. is 20 ° or less.
(2)無機酸化物からなる表面と金属からなる表面の双方を有する封止対象に本発明の組成物を適用する場合において,金属表面に適用された組成物が無機酸化物表面にフローするのを抑制しようとする場合:次の条件Bを満たす組成物であること。
条件B:250℃におけるコバール板への接触角が40°以下で且つガラス板への接触角とコバール板への接触角との差(Δガラス−Kovar)が5°超であるか,又は300℃におけるコバール板への接触角が20°以下で且つガラス板への接触角とコバール板への接触角との差(Δガラス−Kovar)が5°超。(2) When the composition of the present invention is applied to a sealing object having both a surface made of inorganic oxide and a surface made of metal, the composition applied to the metal surface flows to the surface of the inorganic oxide. When it is going to suppress: It is a composition satisfying the following condition B.
Condition B: The contact angle to the Kovar plate at 250 ° C. is 40 ° or less, and the difference between the contact angle to the glass plate and the contact angle to the Kovar plate (Δ glass-Kovar) is more than 5 °, or 300 The contact angle to the Kovar plate at 20 ° C. is 20 ° or less, and the difference between the contact angle to the glass plate and the contact angle to the Kovar plate (Δ glass-Kovar) exceeds 5 °.
(3)無機酸化物からなる表面と金属からなる表面の双方に同時に適用する場合であって,無機酸化物表面と金属表面とを接合する場合:上記条件Aは満たすが,条件Bは満たさない組成物であること。 (3) When applying to both the surface made of inorganic oxide and the surface made of metal at the same time, and joining the surface of the inorganic oxide and the metal surface: Condition A is satisfied, but condition B is not satisfied It must be a composition.
本発明の組成物を用いて封止するとき,作業雰囲気は酸素を含んでいてもいなくてもよい。封止に際しては,封止対象に圧力をかけて接着性を更に高めることもでき,また,封止材に超音波等の振動を与えて融解を促進させることもできる。 When sealing with the composition of the present invention, the working atmosphere may or may not contain oxygen. At the time of sealing, pressure can be applied to the object to be sealed to further enhance the adhesion, and vibration such as ultrasonic waves can be applied to the sealing material to promote melting.
本発明の封止材は種々の電子部品の封止に使用できる。例えば,水晶振動子,半導体素子,SAW素子,有機EL素子に使用できる。 The sealing material of the present invention can be used for sealing various electronic components. For example, it can be used for a crystal resonator, a semiconductor element, a SAW element, and an organic EL element.
更に,本発明の低融点組成物は金属への濡れ性が良いため,金属粉末にこれを添加混合することにより,電気配線,回路形成のための導電用材料を得ることができる。例えば,金属粉末と,これに対し0.5〜5体積%程度の低融点組成物粉末と,意図する粘性に応じた量の溶剤とを含有する組成物を,導電用材料として使用できる。必要に応じてこれにバインダー樹脂を含有させてもよい。また,本発明の組成物のうち,無機酸化物に対する濡れ性も良いものは,アルミナ基板等の酸化物基板上への電気配線,回路形成に好適に用いることができる。 Furthermore, since the low-melting-point composition of the present invention has good wettability to metal, a conductive material for electric wiring and circuit formation can be obtained by adding and mixing it with metal powder. For example, a composition containing a metal powder, a low melting point composition powder of about 0.5 to 5% by volume with respect to this, and a solvent in an amount corresponding to the intended viscosity can be used as the conductive material. You may make this contain a binder resin as needed. Of the compositions of the present invention, those having good wettability to inorganic oxides can be suitably used for electrical wiring and circuit formation on an oxide substrate such as an alumina substrate.
上記において,金属粉末として,銀,銅,アルミニウムを特に好適に使用できるが,これらに限定されない。 In the above, silver, copper, and aluminum can be particularly preferably used as the metal powder, but are not limited thereto.
本発明の導電用材料は,例えばシリコン太陽電池,圧電素子等,種々の電子部品の電極形成や配線に使用できる。 The conductive material of the present invention can be used for electrode formation and wiring of various electronic parts such as silicon solar cells and piezoelectric elements.
本発明の封止材12を用いた水晶振動子の構造を,分解した状態で図4に模式的に示す。また,図5は,本発明の導電用材料を電極に用いた太陽電池の断面を示す模式図である A structure of a crystal resonator using the sealing material 12 of the present invention is schematically shown in FIG. 4 in an exploded state. FIG. 5 is a schematic view showing a cross section of a solar cell using the conductive material of the present invention as an electrode.
以下,実施例を参照して本発明の特徴をより具体的に説明するが,本発明がそれらの実施例に限定されることは意図しない。 Hereinafter, the features of the present invention will be described more specifically with reference to examples. However, the present invention is not intended to be limited to these examples.
〔組成物1〜39〕
表1−1〜1−3に従い,各組成物につき示された配合割合で合計5gとなるように原料を秤取・配合し,乳鉢で粉砕・混合して粉末とした。得られた粉末5gを磁製ルツボに入れた。ルツボを大気中,表に示した溶融温度(500℃又は600℃)に加熱した炉内へ入れ,10分間保持して原料混合物を溶融した。融液を室温にてグラファイト板上へ流し出して冷却させることにより,バルクとして各組成物を得た。[Compositions 1 to 39]
According to Tables 1-1 to 1-3, the raw materials were weighed and blended so that the blending ratios indicated for each composition were 5 g in total, and pulverized and mixed in a mortar to obtain powder. 5 g of the obtained powder was put in a magnetic crucible. The crucible was put in a furnace heated to the melting temperature (500 ° C. or 600 ° C.) shown in the table in the atmosphere and held for 10 minutes to melt the raw material mixture. Each composition was obtained as a bulk by pouring the melt onto a graphite plate at room temperature and allowing it to cool.
〔物性の評価〕
上記で得られた各バルクについて,下記の方法により物性を評価した。[Evaluation of physical properties]
About each bulk obtained above, the physical property was evaluated by the following method.
1.濡れ性の評価
組成物1〜39の各バルクを,直径3mm×高さ5mmの円柱状に切削加工してサンプルとした。各サンプルを25mm角,1.3mm厚のガラス板(ソーダライムガラス)の非錫面(フロートガラス製造時の空気側の面)に立てて載せ電気炉へ入れた。5℃/分で250℃又は300℃まで昇温した後,同温度で1時間保持し,加熱を止め,サンプルを放冷した。ガラス板上のサンプルの形状を観察し,図1に記載の各パラメータを計測し,それらを用いてθ/2法により接触角θを算出した。1. Evaluation of wettability Each bulk of the compositions 1 to 39 was cut into a cylindrical shape having a diameter of 3 mm and a height of 5 mm to obtain a sample. Each sample was placed on a non-tin surface (surface on the air side during the production of float glass) of a 25 mm square, 1.3 mm thick glass plate (soda lime glass) and placed in an electric furnace. The temperature was raised to 250 ° C. or 300 ° C. at 5 ° C./minute, then held at that temperature for 1 hour, heating was stopped, and the sample was allowed to cool. The shape of the sample on the glass plate was observed, each parameter shown in FIG. 1 was measured, and the contact angle θ was calculated by the θ / 2 method using them.
上記と同様の評価を,ガラス板に代えて10mm角,0.2mm厚のコバール板を用いても行うと共に,ガラス板及びコバール板での接触角の間の差〔Δ(ガラス−Kovar)〕も求めた。 The same evaluation as above was performed even when a 10 mm square and 0.2 mm thick Kovar plate was used instead of the glass plate, and the difference between the contact angles of the glass plate and the Kovar plate [Δ (glass-Kovar)] Also asked.
<結果>
各組成物について,ガラス板との接触角,コバール板との接触角,及び両接触角の差を表2−1〜2−3に示す。<Result>
About each composition, the contact angle with a glass plate, the contact angle with a Kovar plate, and the difference of both contact angles are shown to Tables 2-1 to 2-3.
表2−1〜2−3に見られるように,組成物2〜10,12〜13,16〜18,20〜26,29〜30,32,36,38〜39(実施例)は,何れも上記条件Aを満たす。このことは,それら実施例の組成物が何れも金属の封止に好適に使用できるものであることを示している。また,金属への濡れ性が良いことから,金属粉末の焼結助剤としても,また低温焼成の可能な導電用材料の製造にも用いることができる。他方,組成物1,11,14〜15,19,27〜28,31,33〜35,及び37(比較例)は,コバール板への接触角が大きく,金属表面に対する封止材としては好ましくない。 As can be seen from Tables 2-1 to 2-3, the compositions 2 to 10, 12 to 13, 16 to 18, 20 to 26, 29 to 30, 32, 36, 38 to 39 (Examples) Also satisfies the above condition A. This indicates that any of the compositions of these examples can be suitably used for metal sealing. Further, since the wettability to metal is good, it can be used as a sintering aid for metal powder and also for the production of conductive materials that can be fired at low temperature. On the other hand, compositions 1, 11, 14-15, 19, 27-28, 31, 33-35, and 37 (comparative example) have a large contact angle to the Kovar plate and are preferable as a sealing material for the metal surface. Absent.
実施例の組成物のうち,特に組成物2〜7,9〜10,12〜13,16〜18,20〜21,23〜26,30,32,36,及び38〜39は,上記条件Bを満たす。このことは,それらの実施例の組成物が封止対象の金属表面同士を封止により接合させる場合において,接合部の周囲に無機酸化物表面が存在しても,無機酸化物表面に低融点組成物がフローするのを抑制できることを示している。 Among the compositions of the examples, in particular, the compositions 2 to 7, 9 to 10, 12 to 13, 16 to 18, 20 to 21, 23 to 26, 30, 32, 36, and 38 to 39 are based on the above condition B. Meet. This is because when the compositions of these examples are used to seal metal surfaces to be sealed together, even if an inorganic oxide surface exists around the joint, a low melting point is present on the surface of the inorganic oxide. It shows that the composition can be prevented from flowing.
実施例の組成物のうち,特に組成物8,22,及び29は,無機酸化物と金属との異種材料接合において,信頼性の高い封止を行うことを可能にする。 Among the compositions of the examples, the compositions 8, 22 and 29 in particular enable highly reliable sealing in the dissimilar material bonding between the inorganic oxide and the metal.
2.Heリーク試験
標準の金属製半導体パッケージの規格によるTO−5型で,上部に開口のある金属製キャップ(本体はコバール製であり,表面にNiメッキを施したもの)の上部を,300℃に加熱した上記組成物2の融液に漬け,次いで組成物が付着した上部を上側に向けて金属キャップを台上に置いた(図2)。石英ガラス板を,金属キャップ上部に付着した組成物の上に載せ,その状態でそれらを300℃に設定した炉に投入した。炉を300℃で10分間保持後,組成物により封止された金属キャップを炉から取り出し放冷した。金属キャップと石英ガラスは固着していた(図3)。2. He leak test A TO-5 type standard with a standard metal semiconductor package, with the top of a metal cap with an opening at the top (the body is made of Kovar with Ni plating on the surface) at 300 ° C. It was immersed in the melt of the composition 2 that was heated, and then a metal cap was placed on the table with the upper part to which the composition was attached facing upward (FIG. 2). A quartz glass plate was placed on the composition adhering to the top of the metal cap, and in that state, they were put into a furnace set at 300 ° C. After holding the furnace at 300 ° C. for 10 minutes, the metal cap sealed with the composition was taken out of the furnace and allowed to cool. The metal cap and quartz glass were fixed (FIG. 3).
<Heリーク評価方法>
Heリーク試験には,JIS Z 2331:2006に規定された真空吹付け法を用いた。リークディテクタにはHELIOT700((株)ULVAC製)を用いた。このことは当該組成物がコバール(金属)表面とガラス(無機酸化物)表面の両方に隙間なく密着して優れた密封状態を作り出したことを示している。<He leak evaluation method>
For the He leak test, the vacuum spray method defined in JIS Z 2331: 2006 was used. HELIOT700 (manufactured by ULVAC) was used as the leak detector. This indicates that the composition adhered to both the Kovar (metal) surface and the glass (inorganic oxide) surface without any gaps, creating an excellent sealed state.
本発明の低融点組成物は,水晶振動子,LED素子のような電気電子部品に用いる封止材に用いることができ,有用である。また,低融点組成物を焼結助剤として金属へ混合することで,電極および配線のパターニングに用いる導電用材料を作製することができ,有用である。 The low-melting-point composition of the present invention can be used for a sealing material used for electric and electronic parts such as a crystal resonator and an LED element, and is useful. Moreover, a conductive material used for patterning electrodes and wiring can be produced by mixing a low melting point composition with a metal as a sintering aid, which is useful.
10 蓋
12 封止材
14 セラミック基板
16 水晶振動子
20 表面電極
22 反射防止膜
24 アモルファスシリコン
26 裏面電極DESCRIPTION OF SYMBOLS 10 Cover 12 Sealing material 14 Ceramic substrate 16 Crystal oscillator 20 Surface electrode 22 Antireflection film 24 Amorphous silicon 26 Back surface electrode
Claims (11)
Mg,Ca,Sr,Ba,Y,ランタノイド,Ti,Zr,Nb,Ta,Mn,Fe,Co,Zn,B,Ga,In,Si,Ge,Sn,Bi,及びTeからなる群M2より選ばれる1種又は2種以上の構成要素と,
構成要素Ag,I,及びOと
を含んでなる低融点組成物であって,
所定質量の該組成物中,
(a) 正のイオン価を有する全原子のモル数の和に対し,群M1に属する原子のモル数の合計の占める割合が5〜30%,Ag原子のモル数の占める割合が69〜92%であり,
(群M2に属する原子のモル数の合計)/(群M1に属する原子のモル数の合計)が0.01〜0.7であり,
(b) 負のイオン価を有する全原子のモル数の和に対し,I原子のモル数の占める割合が15〜65%,O原子のモル数の占める割合が35〜85%であり,
(c) 負のイオン価を有する全原子のモル数の和に対しI及びOの各原子のモル数の和の占める割合が少なくとも90%であり,そして
(d) Pb原子,F原子及びCl原子の各含有量が何れも1000ppm未満である,
低融点組成物。One or two components selected from the group M1 consisting of Mo and P;
Selected from the group M2 consisting of Mg, Ca, Sr, Ba, Y, lanthanoid, Ti, Zr, Nb, Ta, Mn, Fe, Co, Zn, B, Ga, In, Si, Ge, Sn, Bi, and Te One or more components to be
A low melting point composition comprising components Ag, I, and O,
In a predetermined mass of the composition;
(a) The ratio of the total number of moles of atoms belonging to the group M1 to the sum of the number of moles of all atoms having a positive ion valence is 5 to 30%, and the ratio of the number of moles of Ag atoms is 69 to 92 %,
(Total number of moles of atoms belonging to group M2) / (total number of moles of atoms belonging to group M1) is 0.01 to 0.7,
(b) The ratio of the number of moles of I atoms to the sum of the number of moles of all atoms having a negative ionic valence is 15 to 65%, and the ratio of the number of moles of O atoms is 35 to 85%.
(c) the proportion of the sum of the number of moles of each atom of I and O to the sum of the number of moles of all atoms having a negative ionic valence is at least 90%; and
(d) Each content of Pb atom, F atom and Cl atom is less than 1000 ppm,
Low melting point composition.
Mg,Ca,Sr,Ba,Y,La,Ti,Zr,Nb,Ta,Mn,Fe,Co,Zn,B,In,Si,Ge,Sn,及びTeからなる群M3より選ばれる1種又は2種以上の構成要素と,
構成要素Ag,I,及びOと
を含んでなる低融点組成物であって,
所定質量の該組成物中,
(a) 正のイオン価を有する全原子のモル数の和に対し,群M1に属する原子のモル数の合計の占める割合が5〜30%,Ag原子のモル数の占める割合が69〜92%であり,
(群M3に属する原子のモル数の合計)/(群M1に属する原子のモル数の合計)が0.01〜0.7であり,
(b) 負のイオン価を有する全原子のモル数の和に対し,I原子のモル数の占める割合が15〜65%,O原子のモル数の占める割合が35〜85%であり,
(c) 負のイオン価を有する全原子のモル数の和に対しI及びOの各原子のモル数の和の占める割合が少なくとも90%であり,そして
(d) Pb原子,F原子及びCl原子の各含有量が何れも1000ppm未満である,
低融点組成物。One or two components selected from the group M1 consisting of Mo and P;
One selected from the group M3 consisting of Mg, Ca, Sr, Ba, Y, La, Ti, Zr, Nb, Ta, Mn, Fe, Co, Zn, B, In, Si, Ge, Sn, and Te, or Two or more components,
A low melting point composition comprising components Ag, I, and O,
In a predetermined mass of the composition;
(a) The ratio of the total number of moles of atoms belonging to the group M1 to the sum of the number of moles of all atoms having a positive ion valence is 5 to 30%, and the ratio of the number of moles of Ag atoms is 69 to 92 %,
(Total number of moles of atoms belonging to group M3) / (total number of moles of atoms belonging to group M1) is 0.01 to 0.7,
(b) The ratio of the number of moles of I atoms to the sum of the number of moles of all atoms having a negative ionic valence is 15 to 65%, and the ratio of the number of moles of O atoms is 35 to 85%.
(c) the proportion of the sum of the number of moles of each atom of I and O to the sum of the number of moles of all atoms having a negative ionic valence is at least 90%; and
(d) Each content of Pb atom, F atom and Cl atom is less than 1000 ppm,
Low melting point composition.
Ce,Ga及びBiからなる群M4より選ばれる1種又は2種以上の構成要素と,
構成要素Ag,I,及びOと
を含んでなる低融点組成物であって,
所定質量の該組成物中,
(a) 正のイオン価を有する全原子のモル数の和に対し,群M1に属する原子のモル数の合計の占める割合が5〜30%,Ag原子のモル数の占める割合が69〜92%であり,
(群M4に属する原子のモル数の合計)/(群M1に属する原子のモル数の合計)が0.01〜0.7であり,
(b) 負のイオン価を有する全原子のモル数の和に対し,I原子のモル数の占める割合が15〜65%,O原子のモル数の占める割合が35〜85%であり,
(c) 負のイオン価を有する全原子のモル数の和に対しBr,I,及びOの各原子のモル数の和の占める割合が少なくとも90%であり,そして
(d) Pb原子,F原子及びCl原子の各含有量が何れも1000ppm未満である,
低融点組成物。One or two components selected from the group M1 consisting of Mo and P;
One or more components selected from the group M4 consisting of Ce, Ga and Bi;
A low melting point composition comprising components Ag, I, and O,
In a predetermined mass of the composition;
(a) The ratio of the total number of moles of atoms belonging to the group M1 to the sum of the number of moles of all atoms having a positive ion valence is 5 to 30%, and the ratio of the number of moles of Ag atoms is 69 to 92 %,
(Total number of moles of atoms belonging to group M4) / (total number of moles of atoms belonging to group M1) is 0.01 to 0.7,
(b) The ratio of the number of moles of I atoms to the sum of the number of moles of all atoms having a negative ionic valence is 15 to 65%, and the ratio of the number of moles of O atoms is 35 to 85%.
(c) the proportion of the sum of the number of moles of Br, I, and O atoms relative to the sum of the number of moles of all atoms having a negative ionic valence is at least 90%; and
(d) Each content of Pb atom, F atom and Cl atom is less than 1000 ppm,
Low melting point composition.
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