CN1090800C - Ceramic capacitor - Google Patents
Ceramic capacitor Download PDFInfo
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- CN1090800C CN1090800C CN96104313A CN96104313A CN1090800C CN 1090800 C CN1090800 C CN 1090800C CN 96104313 A CN96104313 A CN 96104313A CN 96104313 A CN96104313 A CN 96104313A CN 1090800 C CN1090800 C CN 1090800C
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- Prior art keywords
- ceramic capacitor
- boron
- borate
- solution
- frit
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- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000000919 ceramic Substances 0.000 claims abstract description 41
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052796 boron Inorganic materials 0.000 claims abstract description 34
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004327 boric acid Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims description 38
- 229910052802 copper Inorganic materials 0.000 claims description 38
- 239000002002 slurry Substances 0.000 claims description 37
- 238000009835 boiling Methods 0.000 claims description 19
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- MLSKXPOBNQFGHW-UHFFFAOYSA-N methoxy(dioxido)borane Chemical compound COB([O-])[O-] MLSKXPOBNQFGHW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 2
- 229960002645 boric acid Drugs 0.000 claims 4
- 235000010338 boric acid Nutrition 0.000 claims 4
- 239000005385 borate glass Substances 0.000 claims 2
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 4
- -1 boric acid ester Chemical class 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 15
- 229910052709 silver Inorganic materials 0.000 description 14
- 239000004332 silver Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 150000001639 boron compounds Chemical class 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 3
- 230000003064 anti-oxidating effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000004455 differential thermal analysis Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229940116411 terpineol Drugs 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- SENLYPZUIGAOEP-UHFFFAOYSA-N B(OC)(O)O.B(OC)(O)O.B(OC)(O)O.B(OC)(O)O.B(OC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O Chemical compound B(OC)(O)O.B(OC)(O)O.B(OC)(O)O.B(OC)(O)O.B(OC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O.B(OCCCC)(O)O SENLYPZUIGAOEP-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- NVEBCPBSGYHFMT-UHFFFAOYSA-N [Zn].[Pb].[B] Chemical compound [Zn].[Pb].[B] NVEBCPBSGYHFMT-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000007767 bonding agent Substances 0.000 description 1
- RRNBWUQDBNKYQG-UHFFFAOYSA-N boric acid;tetrahydrate Chemical compound O.O.O.O.OB(O)O RRNBWUQDBNKYQG-UHFFFAOYSA-N 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- NOXNXVPLDITALF-UHFFFAOYSA-N butoxyboronic acid Chemical class CCCCOB(O)O NOXNXVPLDITALF-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000035900 sweating Effects 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- ZFZQOKHLXAVJIF-UHFFFAOYSA-N zinc;boric acid;dihydroxy(dioxido)silane Chemical compound [Zn+2].OB(O)O.O[Si](O)([O-])[O-] ZFZQOKHLXAVJIF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Ceramic Capacitors (AREA)
- Glass Compositions (AREA)
- Conductive Materials (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
Disclosed is a ceramic capacitor of which capacitance is large and dielectric loss is small, the ceramic capacitor comprises dielectric ceramic and electrodes that are formed on ceramic by baking conductive paste. The conductive paste consisting of substance containing copper powder, glass flit, an organic vehicle, and any of boric acid ester organic matter solution, boric acid solution, and solution of organic salt of boron.
Description
The present invention relates to ceramic capacitor, the ceramic capacitor of the copper electrode of being made by roasting method is particularly arranged.
A kind of ceramic capacitor has dielectric ceramic body and a pair of electrode that is positioned at the dielectric ceramic body.Usually, silk screen printing is made the silver slurry that conductive component and low-melting glass material are made by thin silver powder on the dielectric ceramic body, and the coated silver slurry of roasting is made electrode then.The roasting silver electrode is easy to make, and has good electrical characteristics, as high frequency characteristics and high reliability.
The shortcoming of common silver ink firing electrode is, because silver-colored valency height.Thereby limited the reduction manufacturing cost.Another shortcoming is, is easy to occur the scolder corrosion, when promptly easily wire is soldered to the silver ink firing electrode, and the phenomenon in the silver diffusion charging.Thereby cause the poor adhesive force of electrode, the characteristic variation reduces the capacitance of capacitor.
In addition, the silver migration appears in common silver ink firing electrode easily.Therefore cause dielectric strength and reliability to reduce.Particularly when the dielectric ceramic body was subjected to thermal shock in welding, silver diffused in the fine crack, had further quickened silver-colored migration.
In order to overcome owing to the shortcoming of using the silver ink firing electrode to produce can be used the burning copper electrode in ceramic capacitor.
For example, openly put down at Japan Patent and disclose the burning copper electrode among the 1-51003.Burning copper electrode is made up of copper powder and frit.Comprise at least a as main component in lead borosilicate, borosilicic acid bismuth and the zinc borosilicate in the frit, described frit is the 2-40vol% of copper powder volume.Copper powder and frit be scattered in prepare slurry in the organic solvent, use silk screen print method, prepared slurry is added on the dielectric ceramic body, then with it in neutral gas (in nitrogen) roasting, make the burning copper electrode.
By this method, usually be higher than 800 ℃ temperature roasting, to constitute fine and close roasting electrode.This is because as the electrode green roasting, and scolder is infiltrated in the electrode, makes it cause adverse effect to capacitance and exit intensity.And, will roasting in neutral atmosphere as underlying metal, copper, to prevent its oxidation.
Thereby, in ceramic capacitor, use when burning copper electrode, the dielectric ceramic body that constitutes ceramic capacitor must be heat-treated at 800 ℃.Yet, in neutral atmosphere, cause the reduction of dielectric ceramic body in the high-temperature roasting meeting, thereby make the capacitance of the capacitor of making little.
For oxidation and the Weldability problem that overcomes copper electrode, Japan Patent is openly put down into 1-36243 and is disclosed a kind of electronic unit, conductive film composition and manufacture method thereof, by the invention of the disclosure, conductive film composition comprises 5 to 40wt% the thin boron powder that weight is copper powder weight.Determine the lower limit (5wt%) of boron powder content, not oxidized to guarantee copper powder (underlying metal).
And Japan Patent is openly put down into and is also disclosed non-oxidizing thick film copper conductor among the 1-220303.Conductor is made 900 ℃ of roastings by the copper slurry of boracic manganese compound.The shortcoming of this slurry is, if roasting at low temperatures, the thick film conductor that can not obtain to have good electric conductivity.Another shortcoming is that the copper electrode of making needs an inorganic phosphate coating.
Japan Patent openly put down into disclose among the 3-176903 a kind of with the copper powder be the base electrocondution slurry.Boron that comprises in the slurry and B
2O
3Be respectively the 3.5-3.9wt% and the 2.0-30.0wt% of the copper powder total weight (100wt%) that adds the boron powder.Determine lower limit, to produce antioxidation.
According to prior art, have the ceramic capacitor that burns copper electrode gratifying electrical property and mechanical performance can not be arranged.
The objective of the invention is, a kind of high performance ceramic capacitor with big capacity and low-dielectric loss is provided.This capacitor has been avoided scolder corrosion and silver migration basically, and has excellent high frequency characteristics, reliability.Weldability and life-span.
Another object of the present invention is, provide a kind of under wet condition after load test its capacitance and dielectric loss have only the highly reliable ceramic capacitor of very little decline.
Ceramic capacitor of the present invention comprises: dielectric ceramic body and the electrode that constitutes on it.Electrode is made through roasting with the electrocondution slurry composition of solution that comprises copper powder, frit, organic carrier and be selected from the organic slat solution of acid ester solution, BAS and boric acid.
The manufacture method of ceramic capacitor of the present invention comprises the steps: to form electrode pattern to adding electrocondution slurry on the dielectric ceramic body on the dielectric ceramic body; The media ceramic body that the electrode pattern of electrocondution slurry is arranged in the temperature roasting that is not higher than 600 ℃.
Fig. 1 is the cross-sectional view of ceramic capacitor of the present invention;
Fig. 2 is the TG (thermogravimetry) of tri butyl boron acid esters and the curve chart of DTA (differential thermal analysis).
Think that the boron compound that comprises in the copper slurry becomes B2O
3, it prevents that copper is by slight oxidizing atmosphere oxidation when roasting. And, if slurry is used for consisting of the compound that electrode for capacitors can not require boron yet. When a large amount of use, certainly oxidation can be prevented but the resistance value increase of electrode, thereby cause capacitance to reduce that dielectric loss increases.
The problem that comprises from relevant technologies as can be known will be with a small amount of boron that is enough to prevent anodizing, so that its electrical property such as static capacity and dielectric loss are constant bad. In other words, the boron compound amount that comprises in the copper slurry does not depend on its weight, and determines in the ratio of its (being boron) with weight of copper most. In order to disperse better a small amount of boron, liquid boride surpasses such as B2O
3And MnB
2Boron or the boride of solid form.
Thereby the 1st aspect of the present invention is ceramic capacitor, comprises dielectric ceramic body and the electrode made of roasting electrocondution slurry thereon, described electrocondution slurry is by copper powder, frit, organic carrier and acid ester solution, BAS, any or its composition formation of the organic slat solution of boron.
The 2nd aspect of the present invention is that wherein acid ester solution is higher boiling or the low boiling acid ester solution in high boiling alcohol is arranged such as the ceramic capacitor of the 1st aspect restriction. Higher boiling described in the present disclosure is on 220 ℃ or its, low boiling is below 220 ℃.
The 3rd aspect of the present invention is the ceramic capacitor as the 1st aspect or the qualification of the 2nd aspect, and wherein the higher boiling point borate is with molecular formula (C
nH
2n+1O)
3B represents, n in the formula 〉=4.
The present invention the 4th aspect is the ceramic capacitor that limited as the 1st aspect or the 2nd aspect, and wherein lower boiling borate is low alkyl group (C
1-5) ester compounds, as, methyl borate, trimethylborate, triethyl borate or triproylborate.
The present invention the 5th aspect is the ceramic capacitor that limited as the 1st aspect, and wherein the organic salt of boron is the basic boron of three second (alkane), dimethylamine borane or borohydride sodium.
The present invention the 6th aspect is the ceramic capacitor that limited as the 1st aspect, wherein in the organic slat solution of acid ester solution, BAS or boron the content of boron be boron and copper total weight 0.01 to 0.5wt%, copper powder content be boron and copper total weight 99.5 to 99.99wt%.In other words, in the per 100 parts copper (pph) 0.01 to 0.5 part boron is arranged.
The present invention the 7th aspect is the ceramic capacitor that limited as the 1st aspect, and wherein the content of solid constituent and organic carrier is respectively 70 to 90wt% and 10 to 30wt%, and copper powder content is 80 to 98wt% in the solid constituent, and frit content is about 2-20wt%.
The present invention the 8th aspect is the ceramic capacitor that limited as the 1st aspect, and wherein the softening point of frit is 350 to 500 ℃.
The present invention the 9th aspect is the ceramic capacitor that limited as the 1st aspect, and wherein the dielectric ceramic body is that barium titanate is the ceramic body of base.
According to the present invention, electrocondution slurry should comprise the frit of afore mentioned rules amount.That is, frit content is more than 2wt%, so that after the roasting, electrocondution slurry can adhere on the dielectric ceramic body well.And frit content should so that electrocondution slurry has enough conductances and dielectric loss, should be able to provide enough capacitances less than 20wt%.Copper powder preferably particle diameter is a copper powder in 0.1 μ m to 10 mu m range with SEM (electronic scanner microscope) test.Do not wish to have the blister copper powder to exist, because it can not tight burning.
According to the present invention, in boron, its content is 0.01wt% to 0.5wt% in the solution of borate, and copper powder content is 99.5wt% to 99.99wt%.For anti-oxidation, the amount of boron must be greater than 0.01wt%, and in order to make its solderability and good conductivity, its content should be less than 0.5wt%.
According to the present invention, electrocondution slurry is formed with the solid constituent (copper powder adds frit) of 90-70wt% and 10 to 30% inertia organic carrier.Organic carrier for example is the ethyl cellulose that is dissolved in the terpineol.Also methylcellulose butyl cellulose or acrylic resin can be dissolved in and make organic carrier in the terpineol.
The frit that is used for electrocondution slurry comprises, for example, and boron-lead-zinc glass.Its softening point should be higher than 350 ℃, so that the viscosity of electrocondution slurry is low, thereby can diffuse into well and adhere well on the ceramic body when roasting.The softening point upper limit of frit is 500 ℃, therefore, can finish roasting at low temperature, and roasted product does not all have negative interaction to adhesive force, exit intensity and dielectric loss.
By the present invention, but electrocondution slurry boronic acid containing ester solution.When 200 ℃ of heating, this borate is separated out glass and is changed into B
2O
3The said B of boron
2O
3The coated copper powder is to prevent copper powder oxidation in slight oxygen atmosphere when the roasting.Scribble B
2O
3Copper powder soaked at 350 ℃ to 450 ℃ softening frits easily.Therefore, can make copper electrode at 600 ℃ low-temperature bakes, the density of this copper electrode is enough to prevent the scolder infiltration.
Ceramic capacitor of the present invention has the copper electrode of being made by electrocondution slurry, and this electrocondution slurry comprises as any solution in the acid ester solution of the antioxidant of copper, BAS and the boron organic slat solution.Boron compound forms B on copper powder
2O
3Film is to produce anti-oxidation effect.The boron compound consumption is less than consumption of the prior art among the present invention.The electrical property and the physical property of burning copper electrode and silver ink firing electrode are suitable, and ceramic capacitor of the present invention has good high frequency characteristics.
In addition, electrocondution slurry of the present invention can be made copper conductor at about 600 ℃ of low-temperature bakes.Frit and ceramic body can not reduce during roasting in other words.In other words, ceramic body can be because of reduction reduce capacitance, thereby the ceramic capacitor of making has high capacitance and low-dielectric loss.
Example
Describe invention in detail in conjunction with following each example.
Fig. 1 is the cross-sectional view of ceramic capacitor 10 of the present invention.Ceramic capacitor 10 comprises plate shaped dielectric ceramic body 1 and is positioned at a pair of copper electrode 2 of dielectric ceramic body 1.Exit 3 is electrically connected to a pair of copper electrode 2 respectively by scolder 4.Dielectric ceramic body 1 and electrode 2 are coated with outermost resin 5.
Below the method for ceramic capacitor is made in explanation.At first, make the electrocondution slurry that copper electrode is used with following method preparation through roasting.
Particle diameter is that the copper powder of the 80wt% of 1 μ m, the frit of 8wt% and the organic carrier of 12wt% mix, and frit is at least by boron oxide, and a kind of in lead oxide and the zinc oxide is the P of main component
bO-B
2O
3-Z
nO base glass (6-120253 is disclosed as Japanese patent application).Organic carrier is the ethyl cellulose solution in 8% the terpineol.The mixture and the higher boiling point acid ester solution that generate, any solution in low boiling acid ester solution in the high-boiling point alcohol and the B solution in the organic solvent mixes.The amount that contains boron material is, is 0.01-0.5wt% by the atomic wts boron of boron, and corresponding copper powder amount is 99.5-99.99wt%.Then, with three roller mixers all components is fully mixed.
This slurry that is obtained contains the copper powder of 90.9wt% and the frit of 9.1wt%.The total amount of copper powder and frit is 88wt%, and the amount of organic carrier is 12wt%.
With silk screen print method slurry is added on the dielectric ceramic body 1, forms the pair of electrodes figure on two first type surfaces of media ceramic body 1, dielectric ceramic body 1 is made of barium titanate, and its thickness is 0.5mm, and diameter is 14.0mm.Dielectric ceramic body 1 also can be a disclosed ceramic body among the open 60-31793 of Japan Patent.It is by B
aT
iO
3(85-90wt%) CaZrO
3(8.5-12.0wt%), MgTiO
3(being less than 0.5wt%), CeO
2(less than 0.5wt%), Bi
2O
3(0.1-1.0wt%) and SnO
2(0.1-1.0wt%) constitute.
Roasting dielectric ceramic body is 60 minutes afterwards, and sintering temperature rises to 600 ℃ and this temperature insulation 10 minutes in the roasting.Roasting in nitrogen atmosphere.After the roasting, on the dielectric ceramic body, constitute and burn copper electrode 2.With rosin flux two exits 3 are welded respectively on the burning copper electrode 2.At last, the immersion of dielectric ceramic body is equipped with in the groove of outermost resin, burns copper-base 2 and dielectric ceramic body 1 coating one deck outermost resin 5, make ceramic capacitor 10 thereby make.
The ceramic capacitor that is obtained is measured its capacitance, dielectric loss, exit intensity, weldability, scolder infiltration.The results are shown in Table 1.
When drawing the wire that is welded on the electrode (the silk footpath is 0.6mm) by 120mm/ minute speed,, calculate exit intensity by test required power of stripping electrode (thick 0.5mm, diameter 14.0mm) around the ceramic body.
Baked ceramic body immerses to detect by an unaided eye after the solder bath that rosin flux is arranged assesses weldability.Weldability " good " is meant by the face of weld long-pending greater than 90%, and weldability " medium " is meant that weldability " poor " is meant by the face of weld long-pending less than 50% by the long-pending 50-90% of being of the face of weld.
The inconsistent sample of in the table 1 these and the present invention indicates with * number.
Table 1
| Sample number | Borate wt% | Frit (wt%) | Capacitance (nF) | Dielectric loss 1%) | Exit intensity | Weldability | |
| 1 2 * 3 4 5 6 7 8 * 9 * 10 * 11 12 13 14 * 15 * 16 17 18 19 * | Butyl borate butyl borate butyl borate butyl borate butyl borate butyl borate butyl borate butyl borate butyl borate methyl borate methyl borate methyl borate methyl borate methyl borate perborate tetrahydrate perborate tetrahydrate boric acid | 0.005 0.010 0.010 0.050 0.200 0.400 0.500 0.500 0.550 0.005 0.010 0.200 0.500 0.550 0.005 0.010 0.200 0.500 0.550 | 6.0 1.5 6.0 6.0 6.0 6.0 10.0 22.0 6.0 6.0 6.0 6.0 10.0 6.0 6.0 6.0 6.0 10.0 6.0 | 6.5 10.2 14.2 15.5 16.0 15.0 13.5 9.2 8.8 6.2 14.1 16.0 13.1 9.3 6.0 14.2 15.7 12.8 8.7 | 6.8 1.6 1.6 1.0 0.6 1.2 2.0 7.5 8.0 6.8 1.5 0.8 2.2 8.2 7.0 1.5 0.7 2.4 7.9 | 0.1 0.3 2.3 2.5 3.8 2.5 1.3 1.3 0.1 0.0 2.4 2.6 1.2 0.2 0.0 2.2 2.9 1.0 0.1 | The medium good carefully medium difference difference difference of difference difference medium good in the equal difference difference medium good in equal difference |
Table 1 shows that those samples consistent with the present invention have good weldability and exit intensity, and low dielectric loss.
Notice that sample 2 has big capacity and low-dielectric loss, but exit intensity and weldability are poor.Find that also sample 1,8,9,10,14,15 and 19 has the weldability of big dielectric loss and low exit intensity and difference.
Thermogravimetry and differential thermal analysis result show, the boron glassization in about 200 ℃ of butyl borates.As shown in Figure 2.This just produces the effect of copper powder and atmosphere isolation, thereby protection copper is not introduced in the blanket of nitrogen so that the oxygen oxidation that bonding agent decomposes.
As mentioned above, the present invention has following advantage:
The 1st, the electrode that ceramic capacitor of the present invention has electric electrocondution slurry to make, this electrocondution slurry comprise the antioxidant of anti-copper oxidation, as borate, and boric acid, and/or any in the organic salt of boron.Although these boron compound consumptions seldom, on copper electrode, form B
2O
3Thin vitrifying film, not oxidized with protection copper.As a result, low-dielectric loss and high capacitance are arranged.
The 2nd, electrocondution slurry can not reduce in calcination atmosphere at 600 ℃ of low-temperature bakes (or sintering) pottery and frit.Thereby the ceramic capacitor of generation has high capacitance and low-dielectric loss.
The 3rd, the stove short time low-temperature bake (or sintering) that the refractory material that available rates is cheap constitutes is made ceramic capacitor of the present invention.Thereby cost is reduced.There is the ceramic capacitor of copper electrode suitable with the electrical property and the physical property (or high frequency characteristics) of the ceramic capacitor that silver electrode is arranged.
The 4th, ceramic capacitor of the present invention can be avoided silver migration and scolder corrosion basically, thereby, even when the dielectric ceramic body blind crack occurs owing to sweating heat impacts, still can keep high reliability and long-life.
The 5th, ceramic capacitor of the present invention has the sintered electrode that is difficult for stripping off.
The technical staff of the industry can find, also has the embodiment of other particular form under the situation that does not break away from the present invention's spirit and principal character.Now disclosed each embodiment is just in order to illustrate, rather than to the restriction of invention.Except that the described content of specification, the invention scope and all changes of appended claims appointment belong to the scope of protection of present invention.
Claims (13)
1. a ceramic capacitor comprises:
A dielectric ceramic body; With
A pair of electrode on the dielectric ceramic body, electrode is made of the roasting electrocondution slurry, electrocondution slurry comprises copper powder, frit, organic carrier, solution with the organic salt that comprises borate, boric acid, boron or its mixture, wherein, with respect to the total weight of copper powder and frit, the content of frit is 2-20wt%, and the content of boron is the 0.01-0.5wt% of the total weight of boron and copper in the solution of the described organic salt that comprises borate, boric acid, boron or its mixture.
2. by the ceramic capacitor of claim 1, the solution that it is characterized in that the boracic acid esters is a kind of 220 ℃ or more high boiling borate solution in having 220 ℃ or more high boiling alcohol that has.
3. by the ceramic capacitor of claim 2, it is characterized in that 220 ℃ or more high boiling borate formula (C
nH
2n+1O)
3B represents, n in the formula 〉=4.
4. by the ceramic capacitor of claim 1, the solution that the solution that it is characterized in that the boracic acid esters is a kind of borate with the boiling point that is lower than 220 ℃ in having 220 ℃ or more high boiling alcohol.
5. by the ceramic capacitor of claim 4, the borate that it is characterized in that being lower than 220 ℃ boiling point is selected from the material group that methyl borate, trimethylborate, triethyl borate and triproylborate are formed.
6. by the ceramic capacitor of claim 1, it is characterized in that the organic salt of boracic is selected from the material group of being made up of boron triethyl, dimethylamine borane and borohydride sodium.
7. by the ceramic capacitor of claim 1, it is characterized in that the softening point of frit is 350 ° to 500 °.
8. by the ceramic capacitor of claim 1, it is characterized in that the dielectric ceramic body comprises barium titanate.
9. method of making ceramic capacitor comprises following processing step:
The dielectric ceramic surface adds electrocondution slurry, make on the dielectric ceramic body and constitute electrode pattern, electrocondution slurry comprises copper powder, frit, organic carrier and comprise the solution of borate, boric acid, boron organic salt or its mixture, wherein, with respect to the total weight of copper powder and frit, the content of frit is 2-20wt%, and the content of boron is the 0.01-0.5wt% of the total weight of boron and copper in the solution of the described organic salt that comprises borate, boric acid, boron or its mixture; With
The dielectric ceramic body that the electrode pattern of electrocondution slurry is arranged in the temperature roasting that is not higher than 600 ℃.
10. press the method for the manufacturing ceramic capacitor of claim 9, it is characterized in that, deriving by the boron in the solution and next borate glass coating copper powder in about 200 ℃ of temperature during the calcination steps.
11. by the method for the manufacturing ceramic capacitor of claim 9, the solution that the solution that it is characterized in that the boracic acid esters is a kind of borate that has 220 ℃ or more high boiling borate or have a boiling point that is lower than 220 ℃ in having 220 ℃ or more high boiling alcohol.
12. press the method for the manufacturing ceramic capacitor of claim 9, it is characterized in that the softening point of frit is 350 ℃ to 500 ℃.
13. press the method for the manufacturing ceramic capacitor of claim 12, it is characterized in that copper powder is coated by the borate glass that the boron in the solution derives in about 200 ℃ temperature in the roasting.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8408/95 | 1995-01-23 | ||
| JP07008408A JP3079930B2 (en) | 1995-01-23 | 1995-01-23 | Porcelain capacitors |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1135085A CN1135085A (en) | 1996-11-06 |
| CN1090800C true CN1090800C (en) | 2002-09-11 |
Family
ID=11692335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96104313A Expired - Lifetime CN1090800C (en) | 1995-01-23 | 1996-01-23 | Ceramic capacitor |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3079930B2 (en) |
| KR (1) | KR100207897B1 (en) |
| CN (1) | CN1090800C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8129088B2 (en) * | 2009-07-02 | 2012-03-06 | E.I. Du Pont De Nemours And Company | Electrode and method for manufacturing the same |
| CN105957641B (en) * | 2016-06-08 | 2017-11-28 | 天津大学 | The preparation method that a kind of glass fluxing technique copper for ltcc substrate is starched |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4567059A (en) * | 1981-02-27 | 1986-01-28 | Taiyo Yuden Co., Ltd. | Electronconductive paste to be baked on ceramic bodies to provide capacitors, varistors or the like |
| JPH05234415A (en) * | 1992-02-20 | 1993-09-10 | Murata Mfg Co Ltd | Conductive paste |
| US5332596A (en) * | 1992-01-17 | 1994-07-26 | Murata Mfg. Co., Ltd. | Method for anti-oxidizing treatment of copper powder |
-
1995
- 1995-01-23 JP JP07008408A patent/JP3079930B2/en not_active Expired - Lifetime
-
1996
- 1996-01-23 CN CN96104313A patent/CN1090800C/en not_active Expired - Lifetime
- 1996-01-23 KR KR1019960001418A patent/KR100207897B1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4567059A (en) * | 1981-02-27 | 1986-01-28 | Taiyo Yuden Co., Ltd. | Electronconductive paste to be baked on ceramic bodies to provide capacitors, varistors or the like |
| US5332596A (en) * | 1992-01-17 | 1994-07-26 | Murata Mfg. Co., Ltd. | Method for anti-oxidizing treatment of copper powder |
| JPH05234415A (en) * | 1992-02-20 | 1993-09-10 | Murata Mfg Co Ltd | Conductive paste |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1135085A (en) | 1996-11-06 |
| JPH08203774A (en) | 1996-08-09 |
| KR960030273A (en) | 1996-08-17 |
| KR100207897B1 (en) | 1999-07-15 |
| JP3079930B2 (en) | 2000-08-21 |
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