CN85108680A - 低温烧制陶瓷组合物 - Google Patents
低温烧制陶瓷组合物 Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims description 27
- 238000005245 sintering Methods 0.000 claims abstract description 38
- 239000010953 base metal Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
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- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract 12
- 239000011159 matrix material Substances 0.000 claims abstract 2
- 239000010949 copper Substances 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 239000003985 ceramic capacitor Substances 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000007772 electrode material Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229960004643 cupric oxide Drugs 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000006184 cosolvent Substances 0.000 claims 1
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- 229910000510 noble metal Inorganic materials 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
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- 229910052748 manganese Inorganic materials 0.000 description 3
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- 229910052697 platinum Inorganic materials 0.000 description 3
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- SKIIKRJAQOSWFT-UHFFFAOYSA-N 2-[3-[1-(2,2-difluoroethyl)piperidin-4-yl]oxy-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound FC(CN1CCC(CC1)OC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CC2=C(CC1)NN=N2)F SKIIKRJAQOSWFT-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
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- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
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- 239000010931 gold Substances 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910018967 Pt—Rh Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
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- 239000010946 fine silver Substances 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
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- KQFUCKFHODLIAZ-UHFFFAOYSA-N manganese Chemical compound [Mn].[Mn] KQFUCKFHODLIAZ-UHFFFAOYSA-N 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
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- 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
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/43—Electric condenser making
- Y10T29/435—Solid dielectric type
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
- Inorganic Insulating Materials (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
本发明公开的是具有溅金属电极的多层电容器,电极是在温度低于950℃左右与一种氟化锂助熔剂一起烧结而成,在电极的表面上还具有一种基体金属氧化物覆盖层。本发明也公开了用含有氟化锂助熔剂的介电组合物制作这类电极的方法,并通过调节烧结气氛中的氧分压Po2,可避免溅金属的氧化和介电陶瓷体中的金属氧化物的还原。
Description
本发明涉及陶瓷组合物和生产电子元件的工艺,特别是在低烧结温度下生产带贱金属电极的多层陶瓷电容器的工艺。
形式最简单的陶瓷电容器由一个相当薄的圆片或薄层构成。它具有所需要的形状和尺寸,由经过烧制或烧结的陶瓷介电组合物制成。在此薄层相对的两面上有烧结而成的电极。然而在许多情况下,要求使用一种由多层烧制陶瓷片和导电层(即电极)交替组成的电容器。这些交替的电极显露在该电容器的同一侧面,并连接通电,比如可用一终端电极来连接。
生产这类陶瓷电容器的一种已知的典型方法是将一种含有贵金属如铂或钯的电极软膏(有时称作墨汁)敷在一小块合适的陶瓷介电组合物薄片(通常是浇注成形)的上表面,并用加热时可蒸发的有机粘接剂将它们粘合。操作时要使电极软膏只涂敷在薄片的一个边缘上,而使此涂层的另外三边的周围留有清洁的边缘。然后将这种敷以电极软膏的小薄片叠放在一起,依次叠放的小薄片以垂直于其平面的轴线为中心旋转,这样就把电极软膏涂层扩展到此叠层的背面。然后把软膏包复的薄片层适当地压实,并加热以排除或分解陶瓷薄片的有机接合层及电极软膏,同时使介电组合物烧结成为均一的,多层的物体,其相对的两端有依次排列的电极。然后将每个端面上的电极以已知的方式与终端电极接通。用贵金属来制造电极是因为其熔点高于典型的烧结温度,并具有抗氧化的能力。
因为在工艺中必须采用上述贵金属内部电极,所以此种陶瓷电容器价格昂贵。如果能在足够低的温度下进行介电组合物的烧结,以避免银的熔化、蒸发和氧化,那么也可用较便宜的银来作电极。再者,即便银比贵金属便宜,但仍很贵。因而期望得到一种不要求用贵金属或很贵的金属来生产电容器的方法。
在美国专利第4082906号中所公开的方法,采用含LiF的陶瓷介电组合物,并采用在空气中快速低温(≤900℃)的烧结工艺,以避免使用贵金属电极。由于这些材料能在低温进行烧结,有可能制成多层陶瓷电容器,以下简称MLC,它们含有银含量高达100%的内部电极。这种MLC的制造成本显著下降,因为它们不要求使用含有大量贵金属如Pd(钯)、Pt(铂)或Au(金)的电极。然而,在此工艺中不能采用易氧化的贱金属,如铜。
采用廉价金属电极生产陶瓷电容器的另外一些方法已在美国专利第3920781;4386985;4089813号中公开。这些陶瓷介电组合物是采用钛酸钡加上经过选择的改性剂,在还原性或非氧化性气氛中进行高温(≥1300℃)烧结而制成的。这些陶瓷电容器的内部电极是一种熔点高于烧结温度的贱金属,比如镍或镍合金。为防止贱金属在烧结过程中的氧化和随之而来的其电导率的丧失,必须保持非氧化性的气氛。
在这些工艺中的某些情况下,采用BaO:TiO2摩尔比大于1的BaTiO3也很重要,为的是避免介电组合物中的金属氧化物还原而变成导电状态或者恶化介电性质。
还有另一种可以在陶瓷电容器中不使用昂贵的贵金属电极的方法,这就是制成具有空洞的烧结陶瓷体,然后将低熔点贱金属(如铅)注入这些空洞内以形成电极。这类工艺在美国专利№3679950和 3879645中有介绍。
本发明的目的之一是提供能够在非氧化性气氛中进行低温(950℃左右或更低)烧结的介电组合物,并且可以用不昂贵的贱金属电极材料来制成MLC。
本发明的另一个目的是提供一种在非氧化性气氛中使用贱金属电极进行低温(低于950℃左右)烧结的制造陶瓷电容器的方法。在这种非氧化性气氛中需对氧的分压(PO2)进行调节,以避免贱金属的氧化和陶瓷电性质的恶化。
本发明还有另一个目的,系关于陶瓷介电组合物。此组合物可以在降低氧含量的气氛中在超低温度(≤950℃)下烧结成致密的陶瓷体。
本发明中的介电组合物允许采用廉价的贱金属电极,如铜、镍、钴、铁和/或它们的合金,制造出高质量的MLC。与先有技术相比,可以降低制造成本,因为铜、镍、钴、铁及它们的合金比银和贵金属便宜得多。再者,低温烧结减少了能源消耗的费用,增加了工艺设备如窑炉的使用寿命。
业已发现,可在超低温,即700-950℃左右进行陶瓷介电组合物的烧结。此组合物含有钛酸盐化合物,其通用化学分子式为MTiO3,诸如钛酸钡、钛酸锶和钛酸钙。它们的MO∶TiO2摩尔比大于1.00左右,推荐在大约1和1.03之间,最好是1.02左右。再者,要采用液体蒸气相烧结助熔剂LiF或者在烧结过程中可就地形成LiF的原始化合物,如Li2CO3和NH4F的混合物。需调节氧在烧节气氛中的分压(下文记作PO2),以防止贱金属的氧化和介电陶瓷组合物的缺氧。这种方法制成的陶瓷电容器,在其电极表面有一种贱金属氧化物覆盖层,后者据信对这种组件的电性质有显著的作用。这种陶瓷电容器是在降低氧分压Po2的气氛中,将上面提及的陶瓷介电组合物与作为内部电极的铜在温度低于950℃共同烧结而生产出来的。它们具有高的介电常数,其电容(相对于25℃时的电容)随温度的变化为:当温度从10℃到85℃,相应的电容变化为+22%和-56%。这是由美国电子工业协会(EIA)所指定的数值,也是由工业界作为Z5U特性而承认的。
根据本发明,可以利用介电组合物(含有93%至99%(重量)左右的MTiO3,其MO∶TiO2摩尔比在大约1.00和1.07之间)和大约1.5%至7.0%(重量)左右的LiF烧结助熔剂或能够在低于950℃左右烧结过程中形成LiF的原始材料,在氧分压(Po2)得到调节的气氛中使用贱金属电极材料来生产陶瓷电容器。
那些有技术专长的人们将体会到,当化学计量比大于MO时,仅表示某种金属氧化物的过剩。这种金属氧化物能够在钙钛矿晶体结构中占据钡的位置,BaO、SrO、MO和CaO就是这类氧化物。M仅仅是碱土金属离子的集体代表,这些碱土金属离子形成了钙钛矿晶体结构。
本发明实际应用时所采用的钛酸钡(BaTiO3)或类似化合物可以用那些有技术专长的人们所熟悉的各种工艺来生产,而且已经作为商品来供应。本文介绍的实例中所使用的BaTiO3是从高纯碳酸钡和金红石二氧化钛在氨水分散剂中形成的浆液经与二氧化锆研磨后获得的。研磨过的浆液经干燥、雾化,并在1100℃左右进行锻烧。下面的表1中列出此材料试样有关的化学成份。
表 1
氧化物 重量百分比%
BaO 65.5-66.5
TiO232.0-33.5
SiO2<0.01
Al2O3<0.07
Fe2O3<0.006
CaO <0.02
Nb2O5<0.01
ZrO2<0.01
SrO 0.7
BaO∶TiO21.0-1.06
平均粒度 1.0-1.2μm
本发明的助熔剂据信是游离态的Li和F,它们在烧结条件下由LiF分解而形成。所需要的LiF量可直接添加到介电组合物中去,或加到含锂的原始化合物(包括锂盐、LiCO3、LiI、LiBr和LiNbO3)及含氟的原始化合物(如NH4F和MnF2)中。它们可形成助熔效应,这是在工艺条件下把介电组合物的烧结温度降低到约950℃以下所必须。
令人惊喜的是,在本发明中降低了氧分压(Po2)的气氛中所存在的游离氟和氢不会产生氢氟酸,后者会溶解陶瓷材料,致使工艺过程失效。再者,陶瓷的绝缘性能不致由于各种金属氧化物还原成金属而恶化。而这种还原过程是有可能在上述烧结条件下,特别是通过氧分压(Po2)的调节来控制(降低了的)氧含量时出现的。
本发明中的贱金属电极材料包括熔点高于950℃左右的金属和它们的合金,例如锰、钴、铁、镍和所推荐使用的铜。推荐使用铜是因为它的价格低廉,并具有优异的电性质。铜与其他不太贵的电极材料相比,是一种更好的导热和导电材料。电极材料也可以是贱金属的原始材料,即在烧结条件下转化为贱金属。例如,氧化铜在烧结条件下转化为金属铜。
本发明中的非氧化性烧结气氛防止贱金属在烧结过程中的氧化和随之而来的其导电性质的丧失。据信这种非氧化性的烧结气氛还可使电极表面形成贱金属氧化物覆盖层。这种气氛包括H2、NH3、CO/CO2和H2/CO2其中的氧分压(Po2)按本文所公开的资料进行调节。所推荐的一种气氛是92%N2/8%H2加上CO2。这种气氛不会爆炸并易于处置。在烧结气氛中的氧含量(Po2)需进行控制,以防止电极材料在所要求的烧结温度下氧化和介电组合物中的金属氧化物还原。
实例1-9
具有下面表Ⅱ所示配方的介电组合物的制备过程如下:将BaCO3TiO2和LiF添加到100克的BaTiO3中,并加50cc的蒸馏水。将此浆液放入高速Spex涂料搅拌器内彻底混合搅拌10分钟。随后将混合好的浆液干燥形成一块饼,再放入研缽中用研杵进行研磨。将8cc的粘接溶剂(含有26%(重量)的水、26%(重量)的丙烯甘醇和48%(重量)的谷浆)放入研缽和研杵中与此陶瓷粉末混合,然后此混合物通过一个40目的尼龙筛进行造粒。
所得到的混合物圆片直径为1.27cm,厚为0.1至0.15cm,放在不锈钢模子内用每平方英寸38000磅的压力进行压制。将这些圆片放在一个轻量的氧化铝定位器上,在空气中、在850℃到1000℃的温度下烧制2至5小时。
冷却后,将银电极涂敷在圆片上,然后在815℃进行烧制,使其烧结在圆片上。用ES12110A型电容桥,以1KHz测量频率,在从-55℃到+125℃之间的选定的间隔上,对电容(C)、介质损耗因子(DF),和电容(相对于25℃时的电容)随温度的变化(TC)进行测量。然后按照电容基础方程式计算出每个试样的介电常数:
K=5.66×C 1/(D2) ×1012
这里,K=试样的介电常数;
I=圆片的厚度,英寸;
D=圆片的直径,英寸;
C=圆片的电容,法拉。
在下面表Ⅲ中所概括的实例1至9的介电性质显示出本发明的陶瓷组合物能够在低于950℃温度烧结成致密的实体。这类陶瓷体的介电常数(K)一般大于5000,介质损耗因子(DF)一般小于1.5%,电容随温度的变化(TC)满足Z5U标准。
在这些实例中也显示出BaO∶TiO2摩尔比的重要性。当BaO∶TiO2摩尔比小于1.0,如在实例2和3中,陶瓷介电体不能烧结成为致密的实体,因而不能用来生产MLC元件。当BaO∶TiO2摩尔比大于1.07,如在实例7和9中,介电常数低于3000,这种陶瓷组合物在MLC的应用中几乎没有实际价值。然而,采用某些组合物,其摩尔比或较高或较低(不同于在这里专门介绍的那些组合物)可能是有利的。
表 Ⅲ
TC(%)
实例 K DF(%) 15℃ 85℃
1 8360 0.48 +3.2 -57.4
2 不烧结
3 不烧结
4 6860 0.60 +5.6 -51.3
5 5030 0.60 -1.2 -54.0
6 2550 1.05 +21.3 -38.4
7 1850 0.90 +8.4 -8.5
8 2890 0.76 +9.7 -42.9
9 1454 1.12 +14.3 -12.0
实例10-11
介电组合物的配方示于表Ⅳ。
表 Ⅳ
实例BaTiO3,g LiCO3,g LiF,g NH4F,g MnCO3,gMnF2,g
10 975 35.2 0 34.6 0 1.7
11 975 0 15 0 3.97 0
将这些组分混合,并与一种含乙烯丁缩醛、增塑剂和溶解剂的塑料粘接剂体系进行研磨。将此浆液浇注在厚35 μm的聚丙烯薄膜上,干燥后进行剥离。把这种绝缘胶带装上框,用一架TAM CladanTM134打印机进行打印,再用TAM CladanTM109和101型冲压叠层器和刀具依次进行叠层并切成MLC坯件。这种加工MLC另件的工艺在工业界是很熟悉的很了解的。
电极墨汁中加了42%的金属,并使其通过325目(44μm)的筛子。经干燥的打印过的电极胶带厚度为9μm。叠层温度为65℃,叠层压力为140Kgm/cm2。还生产了用铜和纯银内部电极做的样品,并进行了对比评价。
将多层薄片坯件放在轻量压缩的氧化铝定位器上,然后经过一次加热到260℃的熔掉结合剂的循环1。然后用同样的银或铜电极墨汁一直涂敷到这些试样的端头,以连接所有的内部电极。之后将这些试样放入装在一梯度炉(gradient furnace)内的气密管中。
然后这些MLC坯件在降低的氧分压(Po2)的条件下在850℃至950℃进行烧制。由联合碳化物公司的Linde分部供给的高纯92∶8(N2∶H2)和高纯CO2的混合气体通入该气密管,以此造成还原性气氛。总流量接近500cc/min,并用标定过的Fisher-Porter测量仪进行测量和调节。氧的分压(Po2)是根据气体流量比、温度、所用的贱金属,和公布的热动力学数据而计算出来的。梯度炉内的温度用一系列Pt/Pt-Rh(铂/铂-铑)90/10热电偶进行探测和控制。烧结电容器具有5个有效的介电层,其厚度为1.7至1.9mi(密耳)左右。介电常数(K)、介质损耗因子(DF)、绝缘电阻(R)与25℃时的电容(C)的积以及电容(相对于25℃时的电容)随温度的变化(TC)均用实例1至9中所述的同样的仪表进行测量。仍旧是从-55℃到125℃之间选择一定间隔进行这些测量。结果综合于下面的表Ⅴ中。
表 Ⅴ
TC(%)RC 50V,2min
实例 电极 烧制 Po2K DF +15℃ +85℃ 25℃
10 Ag850℃- 10- 6165 7.69 -3.8 -57.8 <100
950℃, 8.8
4h atm
Cu850℃- 10- 5708 3.56 6.7 -60.9 <100
950℃, 8.8
4h atm
11 Ag900℃ 空气 5806 0.91 -4.2 -52.8 2200
4h
850℃
Cu-950℃, 10- 7710 2.83 -2.2 -69.8 4000
4h 9.2
atm
实例10-11显示出MLC实样具有的介质常数大于5000。实例11中的介电组合物还有附加的优点,即具有小于3%的介质消耗角和大于2000的RC量积。实例10和11的TC特性均满足25U技术条件。
在实例10和11中所述的烧结陶瓷组合物的过程中,特别重要的是建立恰当的氧分压PO2。如果PO2高于诸如铜一类的贱金属的临界氧化水平,则金属部分完全被氧化,即生成氧化铜,并失去导电性,不能起到内部电报的作用。这样的MLC坯件是无用的,因为它们的电容将很小,介电性质将很差。每种贱金属的临界Po2值可以从公布的热动力学数据中获得。
再者,如果PO2太低,虽则可防止电极氧化,然而陶瓷体本身将还原成为半导体,即失去其作为介电材料的功能。那样,这些MLC另件就将具有(1)长得很大的晶粒,(2)很低的绝缘电阻,(3)很大的介质损耗因子,以及(4)很差的电压击穿性能,虽然介电常数可能仍然很高。
当PO2处于临界氧化值以下的恰当范围内时,金属离子,例如铜、镍等之类的离子会在某种程度上沿着其晶界扩散到陶瓷介电体内。同时,陶瓷介电体将被还原到一定程度,并释放出氧。据信金属离子可与氧结合形成贱金属覆盖层,即一层金属氧化物绝缘层,诸如Cu2O、NiO。这些氧化物层防止陶瓷体的进一步还原,而且还提供所需要的绝缘电阻。所以,为生产出有效的介电体和MLC电容器,必须使上述两个过程达到恰当的平衡,这可通过恰当的选择陶瓷组合体、电极材料和PO2值来实现。PO2进一步又与气体比和烧结温度有关。
实例10采用银电极,其介电性质表明,陶瓷体的还原要比所要求的更多所以DF是高的,而RC是低的。当采用铜作为电极材料时,铜的扩散和氧化铜覆盖层的形成使DF得到改善。在稍微高一点的氧分压下来烧结试样,可以改善实例10的DF和RC值。
在实例11中,锰离子以MnCO3的形式被引入以BaTiO3-LiF为基的陶瓷体中。锰的当量含量也比实例10中的高,在实例10中锰锰来源于MnF2。实例11的介电性质表明,锰含量的增加使陶瓷在比实例10还稍微低一点的氧分压(PO2)下具有大得多的抗力,而不致变成半导体。
主要由于锰具有多价态(+2,+4,等)以及能够在A和B格位上作为受主离子,通常用在以BaTiO3为基的介电材料中以改善这些材料的绝缘电阻。
在稍微高一点的氧分压下来烧结该试样,可以进一步改善实例11的介电性质。
鉴于本发明是结合着各种最佳实施例(已由这些实例所阐明)来描述的,很显然,除上面提及的之外,熟悉本技术的人们能够不偏离本发明基本特性的条件下,做出各种修改和变动。而申请人要求保护的正是在本发明的真正的精神和有效的范围内对本发明所做的所有更改和变动。
Claims (10)
1、制作陶瓷电容器的一种方法,其特征在于该方法由以下工序组成:
a、由一种介电组合物制成薄片,此介电组合物包括一种MTiO3化合物、一种能够在钙钛矿晶体结构中占据钡的位置的金属氧化物,以及一种氟化锂助溶剂或含有氟化锂的母体材料。在此介电组合物中要求金属氧化物对于TiO2的摩尔比大于1.00左右。
b)至少在薄片的一部份上包复以一种贱金属电极材料;以及
c)将包复好的薄片在温度低于950℃左右进行烧结,以使电极材料表面形成贱金属氧化物覆盖层。
2、在权利要求1所述的方法中,其中烧结是在这样一种气氛中进行的,即其氧分压PO2经过调节,使贱金属避免氧化而又不使介电组份中的金属氧化物产生显著的还原。
3、在权利要求2所述的方法中,其中MTiO3化合物取自含有BaTiO3、CaTiO3和SrTiO3的一组化合物,金属氧化物选自含有BaO、CaO、和SrO的一组金属氧化物,摩尔比在1.00和1.03之间。
4、在权利要求3所述的方法中,其中MTiO3化合物是BaTiO3,贱金属是铜,摩尔比是1.02左右。
5、一种陶瓷电容器,其特征在于它包括由一种组合物烧结而成的多层介电薄层,此组合物包含一种取自含有BaTiO3、CaTiO3、SrTiO3的一组化合物的MTiO3,和一种氟化锂助熔剂或含有氟化锂的原始材料,组合物中的MO与TiO2的摩尔比大于1.00左右,包括由一种贱金属电极材料制成的处于介电质薄层之间的多层电极薄层;还包括一种在电极薄层表面上的贱金属氧化物覆盖层。
6、一种多层陶瓷电容器,其特征在于它包括多层的介电质薄层,在这些薄层之间有多层的基体金属电极薄层,在电极薄层表面上有金属氧化物覆盖层。
7、在权利要求6中所述的多层陶瓷电容器,其中多层介电质薄层是由含有约93-99%(重量)的MTiO3组合物制成的,其MO∶TiO3摩尔比在大约1.00和1.07之间;贱金属选自含锰、铁、镍、钴、铜和它们的合金。
8、在权利要求7中所述的多层陶瓷电容器,其中MTiO3化合物是BaTiO3,基体金属是铜。
9、一种贱金属/陶瓷的结构,其特征在于它包括一种与一介电陶瓷薄层共同烧制而成的贱金属薄层,在它们之间敷有贱金属氧化物覆盖层。
10、按照权利要求9的结构,其中:贱金属是铜,贱金属氧化物是氧化铜。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US665,917 | 1984-10-29 | ||
US06/665,917 US4612600A (en) | 1984-10-29 | 1984-10-29 | Low fire ceramic compositions |
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CN85108680A true CN85108680A (zh) | 1986-09-10 |
CN1006939B CN1006939B (zh) | 1990-02-21 |
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CN85108680.2A Expired CN1006939B (zh) | 1984-10-29 | 1985-10-28 | 一种制造多层陶瓷电容器的方法及所制成的电容器 |
Country Status (4)
Country | Link |
---|---|
US (1) | US4612600A (zh) |
EP (1) | EP0183366A3 (zh) |
JP (1) | JPS61117819A (zh) |
CN (1) | CN1006939B (zh) |
Families Citing this family (15)
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US4766027A (en) * | 1987-01-13 | 1988-08-23 | E. I. Du Pont De Nemours And Company | Method for making a ceramic multilayer structure having internal copper conductors |
DE69034034T2 (de) * | 1989-10-18 | 2003-10-16 | Tdk Corp., Tokio/Tokyo | Keramischer Mehrschicht-Chipkondensator und Verfahren zu seiner Herstellung |
JPH104027A (ja) * | 1996-06-14 | 1998-01-06 | Murata Mfg Co Ltd | 積層型電子部品 |
US5801108A (en) * | 1996-09-11 | 1998-09-01 | Motorola Inc. | Low temperature cofireable dielectric paste |
WO1999056899A1 (en) * | 1998-05-04 | 1999-11-11 | Colorado School Of Mines | Porous metal-containing materials, method of manufacture and products incorporating or made from the materials |
US6309995B1 (en) | 1998-12-31 | 2001-10-30 | Mra Laboratories, Inc. | Magnesium zinc titanate powder with a barium boron lithium silicate flux and a multilayer ceramic COG capacitor made therefrom |
US7556655B2 (en) * | 2003-03-14 | 2009-07-07 | 3M Innovative Properties Company | Method of producing lithium ion cathode materials |
US20050204864A1 (en) * | 2004-03-16 | 2005-09-22 | Borland William J | Thick-film dielectric and conductive compositions |
US7688569B2 (en) * | 2004-03-16 | 2010-03-30 | E. I. Du Pont De Nemours And Company | Thick-film dielectric and conductive compositions |
EP1676814A1 (fr) * | 2004-12-30 | 2006-07-05 | Stmicroelectronics Sa | Matériaux oxydes diélectriques |
KR100674846B1 (ko) * | 2005-03-29 | 2007-01-26 | 삼성전기주식회사 | 유전체용 세라믹분말의 제조방법, 및 그 세라믹분말을이용하여 제조된 적층세라믹커패시터 |
US20060282999A1 (en) * | 2005-06-20 | 2006-12-21 | Diptarka Majumdar | Electrodes, inner layers, capacitors and printed wiring boards and methods of making thereof - part II |
US7531416B2 (en) * | 2005-12-21 | 2009-05-12 | E. I. Du Pont De Nemours And Company | Thick film capacitors on ceramic interconnect substrates |
WO2016007255A1 (en) * | 2014-07-09 | 2016-01-14 | Ferro Corporation | Mid-k ltcc compositions and devices |
KR20240105967A (ko) * | 2022-12-29 | 2024-07-08 | 삼성전기주식회사 | 적층형 전자 부품 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
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US3920781A (en) * | 1971-04-02 | 1975-11-18 | Sprague Electric Co | Method of forming a ceramic dielectric body |
US3760244A (en) * | 1972-08-31 | 1973-09-18 | Illinois Tool Works | Ceramic capacitor and method of forming same |
US3757177A (en) * | 1973-01-15 | 1973-09-04 | Johanson Mfg | Monolithic base metal electrode capacitor |
JPS5721086B2 (zh) * | 1973-09-10 | 1982-05-04 | ||
US4097911A (en) * | 1975-10-06 | 1978-06-27 | Erie Technological Products, Inc. | Base metal electrode capacitor and method of making the same |
GB1478809A (en) * | 1975-11-11 | 1977-07-06 | Standard Telephones Cables Ltd | Monolithic cermic capacitors |
JPS5324600A (en) * | 1976-08-19 | 1978-03-07 | Murata Manufacturing Co | Nonnreducing dielectric ceramic composition |
US4082906A (en) * | 1977-02-14 | 1978-04-04 | San Fernando Electric Manufacturing Company | Low temperature fired ceramic capacitors |
US4121941A (en) * | 1977-11-10 | 1978-10-24 | Matsushita Electric Industrial Co., Ltd. | Low microwave loss ceramics and method of manufacturing the same |
US4308570A (en) * | 1980-02-25 | 1981-12-29 | Sprague Electric Company | High Q monolithic capacitor with glass-magnesium titanate body |
US4386985A (en) * | 1980-06-30 | 1983-06-07 | North American Philips Corporation | Method of making ceramic dielectric for base metal electrode capacitors |
FR2502383A1 (fr) * | 1981-03-18 | 1982-09-24 | Lcc Cice Cie Euro Composant El | Compositions ceramiques dielectriques, condensateurs utilisant de telles compositions et procede de fabrication desdites compositions |
US4377840A (en) * | 1981-07-16 | 1983-03-22 | E. I. Du Pont De Nemours And Company | Screen-printable dielectric composition |
FR2520729B1 (fr) * | 1982-02-02 | 1986-01-31 | Europ Composants Electron | Composition ceramique dielectrique a base de titanate de baryum, d'oxyde de lithium et de fluorure de zinc, condensateur utilisant une telle composition et procede de fabrication de ladite composition |
-
1984
- 1984-10-29 US US06/665,917 patent/US4612600A/en not_active Expired - Fee Related
-
1985
- 1985-10-11 EP EP85307305A patent/EP0183366A3/en not_active Ceased
- 1985-10-23 JP JP60235510A patent/JPS61117819A/ja active Pending
- 1985-10-28 CN CN85108680.2A patent/CN1006939B/zh not_active Expired
Also Published As
Publication number | Publication date |
---|---|
EP0183366A3 (en) | 1986-07-23 |
CN1006939B (zh) | 1990-02-21 |
JPS61117819A (ja) | 1986-06-05 |
EP0183366A2 (en) | 1986-06-04 |
US4612600A (en) | 1986-09-16 |
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