CN101272991A - COG dielectric composition for use with nickel electrodes - Google Patents

COG dielectric composition for use with nickel electrodes Download PDF

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Publication number
CN101272991A
CN101272991A CNA2006800358797A CN200680035879A CN101272991A CN 101272991 A CN101272991 A CN 101272991A CN A2006800358797 A CNA2006800358797 A CN A2006800358797A CN 200680035879 A CN200680035879 A CN 200680035879A CN 101272991 A CN101272991 A CN 101272991A
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dielectric
composition
till
atm
temperature
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CN101272991B (en
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小沃尔特·J.·赛姆斯
莫哈米德·H.·梅盖尔希
伊丽莎白·W.·J.·罗默
麦克·S.·h.·舒
威利布罗德斯·J.·L.·M.·J.·科庞
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Ferro Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • 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
    • C03C3/14—Silica-free oxide glass compositions containing 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/16—Compositions for glass with special properties for dielectric glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G4/1236—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G4/1236—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates
    • H01G4/1245—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates containing also titanates

Abstract

Multilayer ceramic chip capacitors which satisfy COG requirements and which are compatible with reducing atmosphere sintering conditions so that non-noble metals such as nickel and nickel alloys thereof may be used for internal and external electrodes are made in accordance with the invention. The capacitors exhibit desirable dielectric properties (high capacitance, low dissipation factor, high insulation resistance), excellent performance on highly accelerated life testing, and very good resistance to dielectric breakdown. The dielectric layers comprise a strontium ztrconate matrix doped with other metal oxides such as TiO2, MgO, B2O3, CaO, A12O3 SiO2, and SrO in various combinations. Figure 1 is a cross-sectional view of a multilayer ceramic chip capacitor (1) according to an embodiment of the invention External electrodes (4) of the capacitor (1) are disposed on side surfaces of the capacitor chip (1) and in electrical connection with internal electrode layers (3). The capacitor chip (1) has a plurality of alternately stacked dielectric layers (2).

Description

Be used for the COG dielectric composition that uses with nickel electrode
Technical field
The present invention relates to the dielectric composition of zirconium metatitanic acid alkali, more specifically, relate to the dielectric composition of zirconium strontium titanate base, it can be used to form the multi-layer ceramic chip capacitor with the base metal internal electrode that is formed by nickel or nickelalloy.
Background technology
That multi-layer ceramic chip capacitor has been widely used as is miniature, the electronic component of heavy body and high reliability.Along with the demand that increases day by day to high-performance electronic equipment, multi-layer ceramic chip capacitor also is faced with the market requirement of littler size, higher capacity, lower cost and higher reliability.
Generally prepare multi-layer ceramic chip capacitor by forming alternating layer, described alternating layer is formed by slurry that forms internal electrode (paste) and the slurry that forms dielectric layer.Described layer forms usually in the following way, promptly by compressing tablet, printing or similar techniques, then burns till simultaneously.
Usually, internal electrode by conductor for example the alloy of palladium, gold and silver or described metal form.Though palladium, gold and silver are very expensive,, can partly replace these precious metals by using relatively cheap base metal for example nickel and alloy thereof." base metal " is meant any metal except gold and silver, palladium and platinum.If burn till in atmosphere, the base metal internal electrode can become the state of oxidation, and therefore, dielectric layer and interior electrode layer must burn till in reducing atmosphere altogether.But, in reducing atmosphere, burning till and cause dielectric layer to be reduced, this has reduced resistivity.Proposed to use the multi-layer ceramic chip capacitor of unreducible dielectric substance, but this device have more short-life insulation resistance (IR) and low reliability usually.
Electronic Industries Association USA (EIA) has formulated the standard that is used for capacitance temperature factor (TCC), is called as the COG characteristic.Described COG characteristic requirement changes in capacitance in-55 ℃～+ 125 ℃ temperature range is no more than every degree centigrade of 30ppm (± 30ppm/ ℃).It is aging that the COG element does not show electrical capacity.
Summary of the invention
The invention provides a kind of dielectric composition, it can be used to prepare and the compatible ceramic multilayer capacitor of internal electrode that contains base metal such as nickel or nickelalloy.Can prepare following electrical condenser by dielectric composition of the present invention, this electrical condenser shows stable specific inductivity, little dissipation loss and good reliability under the Highly Accelerated Life Test condition.
Dielectric composition of the present invention comprises that mean diameter is the microstructure of the even compact of about 0.5～about 3 microns crystal grain.The grain microstructure of even compact is acquisition reliability height, has the key of the multi-layer capacitor that is thinner than 5 microns dielectric layers.
In one embodiment, dielectric composition of the present invention comprised the hopcalite of strontium, titanium and zirconium before burning till.The oxide compound that can add assisted sintering, for example MgO, B 2O 3And MgO-CaO-SrO-Al 2O 3-SiO 2Another embodiment of the present invention is a kind of electronic installation, and it comprises the composite wafer (multilayer chip) that contains dielectric layer, and described dielectric layer contains strontium zirconate-strontium titanate mixture and magnesium oxide-boron oxide mixture.Another embodiment of the present invention is a kind of electronic installation, and it comprises the composite wafer that contains dielectric layer, and described dielectric layer contains strontium zirconate-strontium titanate mixture and MgO-CaO-SrO-Al 2O 3-SiO 2Mixture.
In another embodiment, the invention provides a kind of method that forms electronic component, it comprises that particle coated with dielectric substance is to substrate; And under the temperature that is enough to the described dielectric substance of sintering, burning till described substrate, wherein said dielectric substance contained the mixture of ingredients (weight percentage) in the table 1 before burning till.Should be understood to, each numerical value (per-cent, temperature etc.) should think that before " approximately " arranged in this article.
The oxide compound prescription of table 1. dielectric composition
SrO ZrO 2 TiO 2 B 2O 3 MgO
wt％ 41.5-48.5 47-55 1-2 0.05-3 0.05-1.5
Another route is to begin with Strontium carbonate powder, titanium dioxide and zirconium white.Oxide compound that can also be by burning till one or more pre-reactions is SrTiO for example 3Or SrZrO 3Prepare described composition.In this, the prescription of table 2 will form with by the approximately uniform dielectric substance of the prepared dielectric substance of the prescription of table 1.
Table 2. is used for the prescription selected of dielectric substance
SrCO 3 TiO 2 ZrO 2 MgO B 2O 3
wt％ 52.0-56.0 1.0-2.0 41.0-45.0 0.05-1.5 0.05-3.0
In another embodiment, dielectric substance contained the mixture of ingredients (weight percentage) in the table 3 before burning till.
The prescription selected of table 3. dielectric composition
SrO ZrO 2 TiO 2 MgO CaO Al 2O 3 SiO 2
wt％ 44.2-45.6 50.2-51.8 1.5-1.6 0.1-0.4 0-0.3 0.3-1.2 0.5-2.2
Another embodiment of the present invention is a kind of multi-layer ceramic chip capacitor, it comprises the alternately stack layer of dielectric substance and internal electrode material, wherein, described internal electrode material contains the transition metal except Ag, Au, Pd or Pt, and described dielectric substance contains the mixture behind any one the sintering in table 1,2 or 3 the prescription.Another embodiment is the dielectric medium slurry (dielectric paste) that comprises the lead-free and cadmium-free of solids part, and wherein said solids partly comprise glass ingredient, and wherein this glass ingredient contained the component of table 1, table 2 or table 3 before burning till.
Aforementioned and other features of the present invention will more fully be described and particularly point out in the claims hereinafter, following specification sheets has elaborated illustrative embodiments more of the present invention, but these embodiments have just been represented the several different mode that principle of the present invention can be employed.
Description of drawings
Fig. 1 is the cross sectional view of the multi-layer ceramic chip capacitor of embodiments of the present invention.
Embodiment
By alternately stack dielectric layer and internal electrode prepare multi-layer chip capacitor to form the thin slice (green chip) of green compact.The interested internal electrode of this paper is to be made of the base metal that comprises nickel or nickelalloy.The dielectric component that contains organic carrier system by wet-milling is produced the dielectric composition that forms dielectric layer.Dielectric composition is deposited on carrier thin film for example polyester or polypropylene; Perhaps be with for example stainless steel, paper; Perhaps substrate aluminum oxide or on glass for example, coated thin film and form thin slice, described thin slice and electrode alternately pile up the thin slice with the formation green compact.
After forming the green compact thin slice, be lower than about 350 ℃ temperature organic carrier is removed by in air atmosphere, being heated to.In case after the organic carrier removal, then, be about 10 in oxygen partial pressure -12～about 10 -8In the wet nitrogen of atm and the reducing atmosphere of hydrogen, under about 1200 ℃～about 1350 ℃ temperature, burn till described green compact thin slice.Can use various type of heating (heating profile) to remove tackiness agent and burn till described thin slice.
The structure of laminated ceramic capacitor is that people are known in the art.Referring to Fig. 1, there is shown the example structure of multi-layer ceramic chip capacitor 1.The outer electrode 4 of electrical condenser 1 is configured in the side of condenser plate 1, and is electrically connected with interior electrode layer 3.Condenser plate 1 has many dielectric layers that alternately pile up 2.Condenser plate 1 is generally rectangle, but its shape is not crucial.Equally, what its size neither be crucial, this condenser plate can have suitable size according to concrete purposes, usually in 1.0～5.6mm * 0.5～5.0mm * 0.5～1.9mm scope.Interior electrode layer 3 is piled up, make that at relative two ends, they alternately come out on the opposite flank of condenser plate 1.That is, one group of interior electrode layer 3 comes out in a side of condenser plate 1, and another group interior electrode layer 3 comes out on the opposite flank of condenser plate 1.An outer electrode 4 is coated on the side of condenser plate 1, and is electrically connected, another outer electrode 4 is coated on the opposite flank of condenser plate 1, and be electrically connected with the interior electrode layer 3 of another group with one group of interior electrode layer 3.
Dielectric layer is formed by dielectric substance, and described dielectric substance is to comprise that by sintering the hopcalite of strontium, titanium and zirconium shown in table 1,2 or 3 forms.Comprise B 2O 3, MgO or MgO-CaO-Al 2O 3-SiO 2The sintering aid of-SrO is useful.
Another route begins with strontium titanate and the strontium zirconate as shown in table 4 or 5.Those skilled in the art be it is evident that, with oxyhydroxide or other forms, for example the above-mentioned oxide compound of carbonate, acetate, nitrate and organometallic compound (for example metal formate, oxalate etc.) has identical effect, as long as needed metal ion provides with needed amount.
Another prescription of table 4. dielectric composition
SrTiO 3 SrZrO 3 B 2O 3 MgO
wt％ 1-7 89-99 0.05-3 0.05-1.5
Table 5. is used for another prescription of dielectric composition
wt％ SrCO 3 SrZrO 3 SrTiO 3 SrO ZrO 2 TiO 2 MgO CaO Al 2O 3 SiO 2
A 50-58 0-0.5 40-46 0.5-3 0.05-1 0-1 0.05-2 0.05-3
B 90-98 2-5 0-1 0.05-2 0-1.5 0.05-2 0.05-3.5
C 92.5-95.4 3.5-3.6 0.1-0.4 0-0.3 0.3-1.2 0-0.3
D 41.5-48.5 47-55 0.5-2.5 0.05-1 0-0.5 0.05-2.5 0.05-3.5
Can have other compounds in described dielectric substance, condition is that these other compounds can not produce injurious effects to dielectric properties.Usually find that these compounds are as impurity.
Dielectric composition has thin crystalline particle herein, and described particle has about 0.5～about 3 microns mean sizes usually, and it is preferred having less than about 0.7 micron grain-size.
Each dielectric layer has the highest about 50 microns thickness.Preferably, each dielectric layer thickness is about 0.5 micron～about 50 microns.More preferably, each dielectric layer thickness is about 2 microns～about 10 microns.Can use composition herein, prepare multi-layer ceramic chip capacitor, to guarantee inducing capacity fading minimum in work-ing life with thin dielectric layer.That the quantity of the dielectric layer that piles up in chip capacitor is generally is about 2～and about 800, be preferably about 3～about 400.
Multi-layer ceramic chip capacitor of the present invention generally can adopt following method preparation: use slurry, by the printing of routine and the thin slice of tabletting method formation green compact, burn till this green compact thin slice.After burning till, make described thin slice (chip) in for example polishing (tumble) dryly in aluminum oxide or the silicon-dioxide of medium, so that its angle cavetto.Then, for example will contain that the electrocondution slurry of copper is coated to two ends, form end electrode (termination) so that the interior electrode that exposes connects together.Then, make described thin slice 800 ℃ down and in nitrogen atmosphere, carry out end electrode and burn till, conductor (for example copper) being sintered to the solid conduction liner at two ends, thereby form multi-layer capacitor.End electrode is an outer electrode 4 as shown in Figure 1.
Dielectric medium slurry:, can obtain to be used to form the slurry of dielectric layer by organic carrier is mixed with dielectric medium raw material disclosed herein.As what above mentioned, when burning till, change into described oxide compound and composite oxides precursor compound also be useful.Dielectric substance can obtain in the following manner: select to contain the compound of these oxide compounds or the precursor of these oxide compounds, then they are mixed in the proper ratio.Measure the ratio of these compounds in the dielectric medium raw material, make after burning till, can obtain needed dielectric layer composition.The dielectric medium raw material is about 0.1 to have usually～and the powder-form of about 3 microns median size uses, and more preferably is about 1 micron or littler.
Organic carrier: organic carrier is to be dissolved in the tackiness agent in the organic solvent or to be dissolved in tackiness agent in the water.The selection of used in this article tackiness agent is not crucial; Conventional for example ethyl cellulose, polyvinyl butanols, ethyl cellulose and hydroxypropylcellulose and combination thereof of tackiness agent suits to use with solvent.Organic solvent neither be crucial, can select from conventional organic solvent according to application-specific method (that is, print process or pressed disc method), and conventional organic solvent has for example diethylene glycol monobutyl ether, acetone, toluene, ethanol, Diethylene Glycol butyl ether; 2,2,4-neopentyl glycol mono isobutyrate (
Figure A20068003587900101
); α-terpinol; β-terpinol; γ-terpinol; Tridecyl alcohol; The Diethylene Glycol ethyl ether (
Figure A20068003587900102
), Diethylene Glycol butyl ether (butyl ) and propylene glycol; And their mixture.With
Figure A20068003587900104
The trade mark product sold can obtain from Yisiman Chemical Company (Eastman Chemical Company, this baud of gold, Tennessee State); With
Figure A20068003587900105
Or
Figure A20068003587900106
Those products that trade mark is sold can obtain from Dow Chemical (DowChemical Company, Midland, the state of Michigan).
In addition, tackiness agent can be selected from polyvinyl alcohol (PVA) or the polyvinylacetate (PVAC) that is used in combination with water.It should be noted that PVA and PVAC ceramic dielectric powder common and boracic can not be compatible.The aqueous slurry (aquesous slurry) that comprises boron-containing glass tends to form serious gelification with PVA and/or PVAC.Therefore, such as disclosed in the present invention, it is particularly important that the ceramic dielectric powder that does not contain boron is handled for water-based slurry.
Organic carrier content for each slurry (dielectric medium slurry or electrode slurry) does not have special restriction.Usually, described slurry contains the tackiness agent of the 1～5wt% that has an appointment and the organic solvent of about 10～50wt%, and surplus is metal component (being used for electrode) or dielectric component (being used for dielectric layer).If desired, each slurry can contain other additives of the highest about 10wt%, for example dispersion agent, softening agent, dielectric medium compound and insulating compound.
Internal electrode: by electro-conductive material is mixed the slurry that obtains being used to form electrode layer with organic carrier.Electro-conductive material used herein comprises conductor conducting metal for example mentioned in this article and alloy, and the various compound that changes conductor when burning till into, for example oxide compound, organometallic compound and resinate.The example of suitable nickel slurry is the EL51-012 nickel slurry that Ferro Corp (Ferro Corporation) produces.
Referring to Fig. 1, the conductor that forms interior electrode layer 3 is not crucial, but the preferred base metal that uses, because the dielectric substance of dielectric layer 2 has anti-reductive performance.Typical base metal comprises nickel and alloy thereof.Preferred nickelalloy contains at least a other metals that are selected from Mn, Cr, Co, Cu and Al.The alloy that contains at least about the nickel of 95wt% is preferred.It should be noted that nickel and nickelalloy can contain phosphorus and other trace componentss (being impurity) of the highest about 0.1wt%.The thickness that can control interior electrode layer is adapting to specific end use, but the highest usually about 5 micron thickness of this layer.Preferably, interior electrode layer has about 0.5～about 5 microns thickness, more preferably about 1～about 5 microns.
Outer electrode: the conductor that forms outer electrode 4 is not crucial, and still preferred cheap metal is copper, nickel and copper alloy or nickelalloy or cupronickel for example, and it randomly contains Mn, Cr, Co or Al.The thickness that can control external electrode layer is adapting to specific end use, but the highest usually about 10～about 50 micron thickness of this layer, preferably about 20～about 40 micron thickness.Can be by preparing the paste that is used to form outer electrode with the identical method that is used for internal electrode.
Then, from slurry that forms dielectric layer and the thin slice (green chip) that forms the pulp preparation green compact of interior electrode layer.Under the situation of printing process, by the form of slurry with layer alternately is printed in polyester film (for example poly terephthalic acid diethyl alcohol ester (the PET)) substrate; Laminar multilayer body is cut into predetermined shape; And it is separated the thin slice of preparation green compact with substrate.The mode that can also use is a pressed disc method, wherein, and by forming green sheet by the slurry that forms dielectric layer; The slurry that forms interior electrode layer is printed on each green sheet; And printed green sheet piled up the thin slice of preparation green compact.After organic carrier is removed from the green compact thin slice, it is burnt till.Can under normal condition, organic carrier be removed, by in air with 0.01 ℃～20 ℃/hour, more preferably about 0.03 ℃～0.1 ℃/hour speed heating, at about 150 ℃～about 350 ℃, preferably about 200 ℃～about 300 ℃, be incubated under more preferably about 250 ℃ temperature, soaking time is about 30～700 minutes, preferably about 200～300 minutes.
Burn till: in the determined atmosphere of type, the green compact thin slice is burnt till then according to the conductor of the slurry that forms interior electrode layer.If interior electrode layer is that firing atmosphere can have about 10 when for example nickel and nickelalloy formed by the base metal conductor -12～about 10 -8The oxygen partial pressure of atm.Should avoid being lower than about 10 in oxygen partial pressure -12Sintering in the atm atmosphere because described conductor is by unusual sintering under so low pressure, and may come off from dielectric layer.Be higher than about 10 in oxygen partial pressure -8Under the situation of atm, interior electrode layer may be oxidized.About 10 -11～about 10 -9The oxygen partial pressure of atm is most preferred.
For burning till, temperature is elevated to about 1150 ℃～about 1350 ℃ from room temperature, more preferably about 1250 ℃～about 1350 ℃ peak temperature.Temperature is kept about two hours to strengthen densification.Lower maintenance temperature does not provide enough densifications, and too high maintenance temperature can cause very large particle.Preferably, in reducing atmosphere, burn till.The firing atmosphere of example comprises wet N 2, perhaps N 2And H 2The moist mixture of gas.The sintering temperature rise rate is about 50 ℃～about 500 ℃/hour, preferably about 200 ℃～300 ℃/hour; Insulation is about 1200 ℃～about 1350 ℃, preferably about 1250 ℃～about 1350 ℃, and more preferably about 1275 ℃～about 1325 ℃.Soaking time is about 0.5～about 8 hours, and preferably about 1～3 hour, rate of cooling was about 50 ℃～500 ℃/hour, preferably about 200 ℃～300 ℃/hour.
Can be continuously or carry out the removal of organic carrier respectively and burn till.If carry out continuously, this process comprises the removal of organic carrier, changes atmosphere and does not cool off, and is heated to firing temperature, keeps specific time under firing temperature, then cooling.If carry out respectively, after removing organic carrier and cooling, the temperature of described thin slice is elevated to sintering temperature, then atmosphere is changed into reducing atmosphere.
By turnble polishing (barrel tumbling) and/or sandblasting, can polish the thin slice of gained at end face, for example in slurry printing that will form dielectric layer or transfer and burn till to form outer electrode (end electrode) before.What can make the slurry that forms dielectric layer burns till that (oxygen partial pressure is about 10 in the exsiccant nitrogen atmosphere -6Atm) down and under about 600 ℃～800 ℃, carried out about 10 minutes～about 1 hour.
If desired, can externally form liner on the electrode by electrochemical plating or other methods well known in the art.Multilayer ceramic chip capacitor of the present invention can be installed on the printed circuit board (PCB), for example by welding.
Embodiment
Providing following examples to be used to illustrate preferred aspect of the present invention, is not to be used for limiting the scope of the invention.
Summary: preparation has the laminated ceramic capacitor of pure nickel electrode and 10 active coatings (every layer is 5～10 micron thickness), and at reducing atmosphere (pO 2Be 10 -11～10 -8Atm) in and at 1275 ℃～1350 ℃ following sintering.Carry out physical property measurement and electrical measurement.Thin slice after burning till shows and surpasses 30 specific inductivity; DF under 1MHz＜0.1%; TCC is less than ± 30ppm/ ℃ in-55 ℃～+ 125 ℃; 25 ℃ of following IR＞10 13Ohm; 125 ℃ of following IR＞10 12Ohm.Dielectric breakdown voltage surpasses the 140V/ micron.Carry out reliability test by under 140 ℃, making described thin slice bear the 300V volts DS.Do not observe fault after 115 hours.
Embodiment 1
By mixing, an amount of oxide compound as shown in table 6 of preparing burden and/or mill in water, form the dielectric composition that is called as precursor 1.With powder and 1% under high shear force (about 5000/min)
Figure A20068003587900131
C (a kind of polymer suspension agent available from RT Vanderbilt company limited (RT Vanderbilt Co., Inc., Norwalk, the Connecticut State)) mixes.With 0.5mm YTZ (stable yttrium oxide zirconium) the mixed powder pearl is ground to granularity D 50Be about 0.65 micron.At 1200 ℃ powder was calcined 5 hours.Then, the method by routine is pulverized the powder after the calcining, to obtain precursor 1.
The prescription of table 6. precursor 1 before calcining
SrCO 3 ZrO 2 TiO 2
wt％ 54.901 43.761 1.337
In addition, after calcining, the composition of precursor 1 can be represented with following formula: SrZr 0.955Ti 0.045O 3According to the prescription in the table 7 with 2MgO3B 2O 3(as Mg (OH) 2And H 3BO 3Combination) join in the precursor 1, as sintering aid.Once more, under high shear force (about 5000/min), make mixed powder mixes, use 0.5mm YTZ pearl to be ground to granularity D 50Be about 0.40 micron.
The prescription of table 7. embodiment 1 dielectric medium powder before burning till
Precursor 1 Mg(OH) 2 H 3BO 3
wt％ 98.377 0.787 0.836
The powder of embodiment 1 contains the combination of the simple oxide listed just like table 8, has the SrZr of the general formula that can selectively be expressed as: 98.979wt% 0.955Ti 0.045O 3The B of the MgO+0.474wt% of+0.547wt% 2O 3
The oxide components of the dielectric medium powder of table 8. embodiment 1
SrO ZrO 2 TiO 2 MgO B 2O 3
wt％ 45.606 51.791 1.583 0.547 0.474
mol％ 48.869 46.669 2.199 1.507 0.756
Final powder has 0.3～1 micron mean particle size.Then the above-mentioned powder of 100g is joined in the organic carrier of 28.8g described organic polyvinyl butanols, toluene and ethanol of comprising.Wet-milling was used for the slurry of casting method (tape casting) in 24 hours with preparation then.Wet slurry is coated on the polyester film to form dielectric medium green compact bands (green tape).The thickness of dielectric medium green compact band is about 5～about 15 microns, and this depends on the concrete testing method that they are carried out.By the silk screen print method of routine, use conventional nickel slurry, nickel electrode is printed onto on the dried dielectric medium green compact band.Make to amount to 10 sheet stacking, and under the temperature of the pressure of 5100psi and 130 (54 ℃), make it bonding, to form the green compact thin slice.After cutting into suitable size, make afterwards in sintering and contraction (being generally 15%～20%) at X and Y direction, lamina dimensions is about 0.12 " (L) * 0.06 " (W) (EIA 1206 sizes) or about 0.08 " (L) * 0.05 " (W) (EIA 0805 size), according to the circulation of burnouting (burn-out cycle) of table 9 the green compact thin slice is heated to remove organic carrier.
Table 9. binder removal condition
Stage Temperature (℃) Time length (min) Atmosphere
Heat up from room temperature 265 1200 Air
Insulation 265 240 Air
Cool to room temperature 25 Reach 25 ℃ Air
For all embodiment, thin slice at first under about 265 ℃ temperature (table 9) remove their tackiness agent, make it then under 1250 ℃～1350 ℃ temperature and at pO 2Be 10 -11～10 -8The N of atm 2/ H 2/ H 2Be sintered in the gaseous mixture of O.By being that 35 ℃ wetting agent makes N with water temperature 2/ H 2Air humidity moistens and obtains described gaseous mixture.Make resulting thin slice corner cavetto by polishing (tunmbling).Will be by (the Ferro Corporation of Ferro Corp, the Cleveland, the Ohio) copper slurry as the commercially available formation outer electrode of TM50-081 of Sheng Chaning is coated on the end face, and burns till about 70 minutes in the exsiccant nitrogen atmosphere and under 775 ℃, to form outer electrode.The multi-layer capacitor of being processed has the size of about 3.2mm * 1.6mm (EIA1206 size) or about 2.1mm * 1.3mm (EIA0805 size), and it has various thickness.Dielectric layer is 6～15 micron thickness, and the interior nickel electrode layer is about 1.5 micron thickness.
Test from the powdered preparation multi-layer chip capacitor of embodiment 1 and to it.Firing condition and electric property are summarized in table 10.Embodiment all in the table 10 (1a-1g) was burnt till under indicated temperature 2 hours.
The firing condition of the MLCC of table 10. embodiment 1 and electric property
Embodiment 1a 1b 1c 1d 1e 1f 1g
Sintering temperature (℃) 1275 1275 1300 1300 1325 1325 1325
pO 2(atm) 10 -10 10 -11 10 -10 10 -11 10 -8 10 -9 10 -10
Dielectric thickness (micron) 5.0 4.7 5.1 5.0 5.2 5.0 5.4
Electrical capacity (pF) 386.5 363.2 412.2 391.8 422.6 418.5 406.5
DF(％) 0.019 0.003 0.007 0.008 0.023 0.013 0.023
Specific inductivity 30.0 27.9 34.8 32.5 38.4 36.3 29.5
TCC(ppm/℃)
25℃ -12.4 -12.2 -6.7 -12.2 -11.6 -8.8 -3.8
85℃ -2.2 -3.8 -0.3 -3.4 -7.8 -1.0 3.3
125℃ -1.8 -2.6 1.0 -2.2 -1.8 0.0 7.0
IR(10 12Ohm)
25℃ 900 760 270 440 390 660 420
125℃ 47.0 8.6 13.0 5.8 6.3 7.5 9.8
Voltage breakdown (V) 1060 945 977 880 1005 811 714
Embodiment 2
According to table 11, with Mg (OH) 2, CaCO 3, Al 2O 3And SiO 2Mixture join in the precursor 1, (after burning till, produce MgO-CaO-Al efficiently as sintering aid 2O 3-SiO 2).Handle this powder according to embodiment 1.
Dielectric prescription of table 11. embodiment 2 before burning till
Precursor 1 Mg(OH) 2 CaCO 3 Al 2O 3 SiO 2
wt％ 97.812 0.257 0.257 0.579 1.096
The powder of embodiment 2 has the SrZr of the general formula that can selectively be expressed as: 98.003wt% 0.955Ti 0.045O 3The Al of the CaO+0.579wt% of the MgO+0.144wt% of+0.178wt% 2O 3The %SiO of+1.096wt 2When representing with the simple oxidation thing, embodiment 2 has the prescription of table 12.
The oxide components of the dielectric medium powder of table 12. embodiment 2
SrO ZrO 2 TiO 2 MgO CaO Al 2O 3 SiO 2
wt％ 45.156 51.281 1.567 0.178 0.144 0.579 1.096
mol％ 48.288 46.115 2.173 0.489 0.285 0.629 2.021
Come the final powder of processing and implementation example 2 according to the process of embodiment 1, be used for the MLCC thin slice of electrical testing with preparation.Firing condition and electric property are summarized in table 13.Make that embodiment 2a-2d burnt till 2 hours in the table 13 under indicated temperature.
The firing condition of the MLCC of table 13. embodiment 2 and electric property
Embodiment 2a 2b 2c 2d
Sintering temperature (℃) 1300 1300 1325 1350
pO 2(atm) 10 -10 10 -11 10 -10 10 -10
Dielectric thickness (micron) 12.3 11.3 11.0 10.9
Electrical capacity (pF) 152.7 158.2 164.7 166.5
DF(％) 0.005 0.070 0.010 0.007
Specific inductivity 31.2 32.3 31.4 31.5
TCC(ppm/℃)
25℃ -4.8 -3.8 0.5 0.2
85℃ 4.5 4.0 7.3 7.2
125℃ 4.5 5.0 8.0 7.6
IR(10 12Ohm)
25℃ 100.0 31.0 5.0 34.0
125℃ 6.5 5.0 2.1 3.0
Voltage breakdown (V) 1726 909 1565 1562
Embodiment 3-14
According to the prescription of the embodiment 3-14 in the table 14, the mixtures of various different amounts are joined in the precursor 1 as sintering aid, described mixture comprises MgO, CaO, Al 2O 3, SiO 2And/or among the SrO any one or all.Because the sintering aid in embodiment 12,13 and 14 also contains SrO, total SrO in these embodiments derives from precursor 1 and sintering aid.For embodiment 3-14, the gross weight of precursor 1 is first three columns (SrO, ZrO 2And TiO 2) sum.For the ease of comparing, the composition of embodiment 2 and MLCC electric property are also included within table 14 and 15.
The oxide components (representing) of the powder of table 14. embodiment 2-14 with wt%
Embodiment SrO ZrO2 TiO2 MgO CaO Al2O3 SiO2 SrO from sintering aid
2 45.156 51.281 1.567 0.178 0.144 0.579 1.095 0
3 44.236 50.236 1.535 0.355 0.288 1.158 2.192 0
4 45.616 51.803 1.583 0.089 0.072 0.290 0.548 0
5 45.160 51.286 1.567 0.204 0.108 0.579 1.096 0
6 45.165 51.291 1.567 0.230 0.072 0.579 1.096 0
7 45.170 51.296 1.567 0.255 0.036 0.579 1.096 0
8 45.174 51.307 1.567 0.281 0.000 0.579 1.096 0
9 45.305 51.450 1.572 0.178 0.144 0.581 0.770 0
10 45.355 51.506 1.574 0.178 0.145 0.582 0.661 0
11 45.405 51.563 1.575 0.179 0.145 0.582 0.551 0
12 45.173 52.265 1.566 0.178 0.108 0.579 1.096 0.036
13 45.190 51.249 1.566 0.177 0.072 0.579 1.095 0.072
14 45.221 51.218 1.565 0.177 0.000 0.578 1.095 0.146
Come the final powder of processing and implementation examples 3-14 according to the process of embodiment 1, be used for the MLCC thin slice of electrical testing with preparation.Firing condition and electric property are summarized in table 15.Each MLCC was burnt till 2 hours.
Firing condition and the electric property of the MLCC of table 15. embodiment 2d-15
Embodiment 2d 3 4 5 6 7 8 9 10 11 12 13 14
Sintering temperature (℃) 1350 1325 1350 1350 1350 1350 1350 1325 1325 1325 1325 1325 1325
pO 2(atm) 10 -10 10 -11 10 -10 10 -10 10 -10 10 -10 10 -10 10 -10 10 -10 10 -10 10 -10 10 -10 10 -10
Dielectric thickness (micron) 10.9 19.0 3.5 10.3 10.7 11.3 10.8 13.0 11.4 12.6 13.5 13.1 12.4
Electrical capacity (pF) 166.5 313.1 502.3 180.2 173.2 166.8 172.8 163.5 169.2 168.9 159.4 163.9 151.5
DF(％) 0.007 0.016 0.012 0.033 0.012 0.006 0.294 0.010 0.011 0.017 0.009 0.015 0.007
Specific inductivity 31.5 31.0 31.0 31.5 31.7 32.0 30.8 35.5 30.6 34.7 37.2 39.8 33.0
TCC (ppm/℃)
25℃ 0.2 -2.4 2.4 -3.7 -5.6 -6.6 -2.8 -4.2 -4.0 1.0 -6.2 -2.0 -7.0
85℃ 7.2 7.0 -2.8 4.3 2.6 2.6 1.6 2.8 3.4 7.0 2.0 6.0 1.2
125℃ 7.6 8.4 10.0 7.6 4.7 3.0 2.2 6.3 4.2 7.0 2.8 6.5 2.0
IR(10 12Ohm)
25℃ 34.0 71 440 85 47 89 17 140 140 250 57 57 98
125℃ 3.0 3.0 1.7 1.8 1.8 1.7 1.2 4.4 2.7 6.4 8.9 2.5 2.1
Voltage breakdown (V) 1562 1663 595 765 1259 1419 401 1892 1605 1735 1533 1036 1578
All have very high specific inductivity, low DF, little grain-size and the high voltage breakdown of burning till from the exemplary sheet of the preparation of compositions of embodiment 1-14.TCC has satisfied the COG standard, and the IR under 25 ℃ and 125 ℃ has surpassed the EIA standard.
For a person skilled in the art, be very easy to find other advantage and improvement.Therefore, the present invention of wider scope aspect is not limited to specific detail and the example that this paper is shown and describe.Thus, do not depart from claims with and the situation of the spirit or scope of the total design of the present invention that counterpart was limited under, can make various improvement.

Claims (20)

1. the dielectric medium slurry of a lead-free and cadmium-free, it comprises the solids part, wherein, described solids part comprised before burning till:
A. the SrO of about 41.5wt%～about 48.5wt%;
B. the ZrO of about 47wt%～about 55wt% 2
C. the TiO of about 0.5wt%～about 2.5wt% 2
D. the MgO of about 0.05wt%～about 1.5wt%; And
E. the B of about 0.05wt%～about 3wt% 2O 3
2. method that forms electronic component comprises:
A. the described dielectric medium slurry of claim 1 is coated in the substrate; And
B. under the temperature of enough described dielectric substances of sintering, burn till described substrate.
3. method according to claim 2, wherein, described burning till under 1200 ℃-1350 ℃ temperature carried out.
4. method according to claim 2, wherein, described to burn till in oxygen partial pressure be about 10 -12Atm～about 10 -8Carry out in the atmosphere of atm.
5. multi-layer ceramic chip capacitor comprises the following aggregate that burns till (collection):
A. the alternately stack layer of the described dielectric substance of claim 1; With
B. the layer of internal electrode material, described internal electrode material comprises the transition metal except Ag, Au, Pd or Pt.
6. multi-layer ceramic chip capacitor according to claim 5, wherein, described internal electrode material comprises nickel.
7. method that forms electronic component comprises:
A. i. is comprised the described slurry of claim 1 the oxycompound dielectric material layer and
Ii. the metallic electrode slurry bed of material
Alternately be coated in the iii. substrate, to form laminar multilayer body;
B. under the temperature of enough described dielectric substances of sintering, burn till described substrate;
C. described laminar multilayer body is cut into predetermined shape;
D. the multilayer body of cutting is separated with substrate; And
E. burn till described multilayer body, with the oxide compound in metal in the sintered electrode and the fusion dielectric substance, wherein, each all has layer thickness described internal electrode and described dielectric substance.
8. method according to claim 7, wherein, described dielectric material layer has about 1 micron～about 50 microns thickness after burning till.
9. method according to claim 7, wherein, described burning till under 1200 ℃～about 1325 ℃ temperature carried out.
10. method according to claim 7, wherein, described to burn till in oxygen partial pressure be about 10 -12Atm～about 10 -8Carry out in the atmosphere of atm.
11. method according to claim 7, wherein, described metallic electrode slurry comprises nickel.
12. the dielectric medium slurry of a lead-free and cadmium-free, it comprises the solids part, and wherein, described solids part comprised before burning till:
A. the SrO of about 44.2wt%～about 45.6wt%;
B. the ZrO of about 50.2wt%～about 51.8wt% 2
C. the MgO of about 0.1wt%～about 0.4wt%;
D. the TiO of about 1.5wt%～about 1.6wt% 2
E. the Al of about 0.3～about 1.2wt% 2O 3
F. the SiO of about 0.5～about 2.2wt% 2And
G. the CaO of the highest about 0.3wt%.
13. a method that forms electronic component comprises:
A. the described dielectric medium slurry of claim 12 is coated in the substrate; And
B. under the temperature of enough described dielectric substances of sintering, burn till described substrate.
14. method according to claim 12 wherein, is describedly burnt till under 1200 ℃～1350 ℃ temperature and is about 10 in oxygen partial pressure -12Atm～about 10 -8Carry out in the atmosphere of atm.
15. a method that forms electronic component comprises:
The particle coated of the dielectric substance after a. will calcining is to substrate; And
B. under the temperature of enough described dielectric substances of sintering, burn till described substrate;
C. wherein, before burning till, described dielectric substance comprises the composition that is selected from the group of being made up of composition 1, composition 2, composition 3 and composition 4, wherein, and before calcining,
I. composition 1 comprises:
1. the SrTiO of about 1wt%～about 7wt% 3,
2. the SrZrO of about 89wt%～about 99wt% 3,
3. the B of about 0.05wt%～about 3wt% 2O 3And
4. the MgO of about 0.05wt%～about 1.5wt%;
Ii. composition 2 comprises:
1. the SrCO of about 52wt%～about 56wt% 3,
2. the ZrO of about 41wt%～about 45wt% 2,
3. the TiO of about 1wt%～about 2wt% 2,
4. the B of about 0.05wt%～about 3wt% 2O 3And
5. the MgO of about 0.05wt%～about 1.5wt%;
Iii. composition 3 comprises:
1. the SrCO of about 50wt%～about 58wt% 3,
2. the ZrO of about 40wt%～about 46wt% 2,
3. the TiO of about 0.5wt%～about 3wt% 2,
4. the MgO of about 0.05～about 1wt%,
5. the Al of about 0.05wt%～about 2wt% 2O 3,
6. the SiO of about 0.05wt%～about 3wt% 2,
7.CaO, its amount be no more than about 1wt% and
8.SrO its amount is no more than about 0.5wt%; And
Iv. composition 4 comprises:
1. the SrTiO of about 2wt%～about 5wt% 3,
2. the SrZrO of about 90wt%～about 98wt% 3,
3. the MgO of about 0.05～about 2wt%,
4. the Al of about 0.05wt%～about 2.5wt% 2O 3,
5. the SiO of about 0.05wt%～about 3.5wt% 2,
6.SrO, its amount be no more than about 1wt% and
7.CaO its amount is no more than about 1wt%.
16. method according to claim 15, wherein, described burning till under 1200 ℃～1350 ℃ temperature carried out.
17. method according to claim 15, wherein, described to burn till in oxygen partial pressure be about 10 -12Atm～about 10 -8Carry out in the atmosphere of atm.
18. method according to claim 15, wherein, described burning till under 1200 ℃～about 1325 ℃ temperature carried out.
19. method according to claim 15, wherein, described dielectric substance comprised composition 1 before burning till.
20. method according to claim 15, wherein, described dielectric substance comprised composition 3 before burning till.
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CN102903949A (en) * 2012-10-13 2013-01-30 苏州征之魂专利技术服务有限公司 New energy power cell structure
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CN102903521A (en) * 2011-07-26 2013-01-30 三星电机株式会社 Multi-layered ceramic electronic component
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