CN101295582B - Conductive paste, conductive paste drying film and multilayer ceramic capacitor employing the same - Google Patents
Conductive paste, conductive paste drying film and multilayer ceramic capacitor employing the same Download PDFInfo
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- CN101295582B CN101295582B CN2008100929474A CN200810092947A CN101295582B CN 101295582 B CN101295582 B CN 101295582B CN 2008100929474 A CN2008100929474 A CN 2008100929474A CN 200810092947 A CN200810092947 A CN 200810092947A CN 101295582 B CN101295582 B CN 101295582B
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Abstract
The invention provides a conductive nickel paste capable of forming thick electrode film with favorable continuity, with an inside electrode using the maximum protuberance height below 1.0 um in the drying film of conductive paste, with a baking film thickness of about 1.0 um, and a multi-layer ceramic capacitor using the paste. The conductive paste of the invention at least comprises a nickel powder with a quality ratio of carbon content below 0.06 percent and an average grain diameter below 0.20 um; and a ceramic powder with an average grain diameter below 0.10 um.
Description
Technical field
The present invention relates to be used to make conductive paste multilayer ceramic capacitor (below be called " MLCC "), that form internal electrode of small-sized, high power capacity, and adopt the laminated ceramic electronic units such as multilayer ceramic capacitor of this paste.
Background technology
MLCC is generally by following such manufacturing.At first, in order to form dielectric layer, containing barium titanate (BaTiO
3) with the dielectric raw cook of organic bond such as polyvinyl butyral resin on (グ リ one Application シ one ト); The conductive paste that is dispersed in the formation internal electrode in the carrier that contains electroconductive powder, resin binder and solvent, with the pattern printing of regulation, drying; Remove and desolvate, form desciccator diaphragm.Secondly, the dielectric raw cook that has printed this conductive paste, add thermocompression bonded with the overlapping state of multilayer and be integrally formed the back cut-out, in oxidizing atmosphere or inert atmosphere, in carrying out the unsticking mixture below 500 ℃.Then, for not oxidation internal electrode, in reducing atmosphere, about 1300 ℃, add thermal bake-out.In addition, the chip of roasting is coated with, after the roasting, externally implements nickel plating etc. on the electrode, accomplish MLCC.
Yet in above-mentioned calcining process, the temperature that the dielectric ceramic powder begins sintering is about 1200 ℃, shrinks the beginning temperature with the sintering of metal dust such as nickel and produces suitable mismatch, so be prone to faults of construction such as generation delamination (splitting) or crack.Particularly be accompanied by miniaturized high capacityization, the lamination number the more or the thickness of ceramic dielectric layer thinner, the generation of fault of construction is significantly.
Therefore; For example paste over nickel at internal electrode; For near the sintering of controlling at least the temperature that sintering until dielectric layer shrinks beginning shrinks; General through adding with the ceramic powders of perofskite type oxides such as the barium titanate class of the composition of similar dielectric layer or strontium zirconate class as principal component, the sintering behavior of control nickel powder, the mismatch of control interior electrode layer and the sintering contraction behavior of dielectric layer.
, be accompanied by the frivolous miniaturization of electronic instruments such as mobile phone or digital instrument, also hope miniaturization, high capacity and high performance as the multilayer ceramic capacitor of chip part.Being used to realize the most effectively means of these requirements, is to make interior electrode layer and dielectric layer attenuate seek multiple stratification.
Therefore; Require the more small-sized high capacity of MLCC in recent years, for example, to adopting the internal electrode of nickel etc.; Inquired into densification and the thin layerization of the good electrode film of continuity; To ceramic dielectric material and adopt its dielectric layer, inquire into high-kization and thin layerization, the dielectric bed thickness reaches the MLCC practicability below the 2.0 μ m.Yet, electrode film is hoped to reach below the 1.0 μ m.
The thin layerization of the roasting electrode film that continuity is good for the densification that realizes above-mentioned internal electrode as the characteristic of necessity, is mainly enumerated following 3 points.That is,
1) internal electrode has high desciccator diaphragm density with the desciccator diaphragm of nickel paste;
2) on the desciccator diaphragm that internal electrode is stuck with paste with nickel, there is not the thrust that runs through the dielectric raw cook;
3) after the internal electrode of thin printing coating was stuck with paste roasting with nickel, electrode film did not break, and the active electrode area is high.
As to above-mentioned 1) detail, exactly as internal electrode have high desciccator diaphragm density with the desciccator diaphragm of nickel paste, then can realize the thin layerization of the laminated chip internal electrode after the roasting.
Promptly; In order to adopt a spot of metal coated amount to form the high density internal electrode; Realize thin layerization and target capacity value simultaneously, when internal electrode was dry with paste, the conductive particle packed density (desciccator diaphragm density) that as far as possible improves per unit volume (or silk screen printing unit are) was a big problem.
In addition, as to above-mentioned 2) detail, exactly for making the dielectric layer thickness attenuation that is accompanied by high capacity, the essential flatness that improves the desciccator diaphragm that internal electrode sticks with paste with nickel.
That is, the height of thrust hour in the desciccator diaphragm that the thickness of dielectric layer raw cook is stuck with paste with nickel than internal electrode produces thrust and runs through ceramic green sheet, between electrode film, produces short circuit, the problem that reliability or the product percent of pass etc. of capacitor are reduced.
In addition; As to above-mentioned 3) detail, be exactly when the bed thickness attenuate, be difficult to guarantee the active electrode area of internal electrode; And the interior electrode layer during roasting becomes more deep with the different of shrinkage of dielectric layer, MLCC is produced the problem that is called the fatal fault of construction of causing of delamination.
According to above-mentioned situation, for example, patent documentation 1 also discloses the scope of the electrode film of impossible formation thickness 1.0 μ m, exists problems such as the thin layerization of electrode film are inappropriate.
In addition, patent documentation 2 discloses the scope that forms below the electrode thickness 0.7 μ m, but the electrode thickness that surpasses this scope is when being 0.8 μ m, if ceramic bed thickness reaches below the 3 μ m problem that exists delamination to take place frequently.
In addition; Patent documentation 3 discloses in the scope below the full-size 4.0 μ m of electrode thickness, more than the minimum dimension 0.2 μ m, and the fluctuation of electrostatic capacitance amount is also little, being suppressed of delamination; But the invention that this patent documentation 3 relates to is inappropriate to the thin layerization of electrode film.
[patent documentation 1] spy opens the 2002-245874 communique
[patent documentation 2] spy opens the 2005-167290 communique
[patent documentation 3] spy opens flat 10-12477 communique
Summary of the invention
The present invention proposes in order to solve these original problems; Provide a kind of internal electrode to reach below the 1.0 μ m with the maximum rising height of the desciccator diaphragm of nickel paste; The nickel of printing coating is thinly stuck with paste and after roasting, can be guaranteed high active electrode area on the dielectric sheet; In addition, the non-structure defective can reach conductive paste, the conductive paste drying film of internal electrode thickness 1.0 μ m left and right sides thin layerizations and the multilayer ceramic capacitor that adopts this paste.
Therefore, the conductive paste that the present invention relates to is characterized in that, its contain at least carbon component content mass ratio below 0.06%, average grain diameter is lower than the nickel powder of 0.20 μ m; And average grain diameter is lower than the ceramic powders of 0.10 μ m.
In addition, another conductive paste that the present invention relates to is characterized in that, its contain at least carbon component content mass ratio below 0.06%, average grain diameter is lower than the nickel powder of 0.20 μ m; Average grain diameter is lower than the ceramic powders of 0.10 μ m; Binder resin; And organic solvent, in addition, above-mentioned relatively nickel by powder 100 mass parts of the containing ratio of above-mentioned ceramic powders are 10～25 mass parts.
In addition, another conductive paste that the present invention relates to is characterized in that, contain at least from the nickel powder that adopts liquid phase method or vapor phase method manufacturing according to the mass ratio of carbon component content 0.06% below, average grain diameter is lower than the nickel by powder of the condition selection of 0.20 μ m; And average grain diameter is lower than the ceramic powders of 0.10 μ m.
In addition, the conductive paste drying film that the present invention relates to is characterized in that, prints above-mentioned conductive paste, and the desciccator diaphragm density of carrying out dry resulting desciccator diaphragm is more than 5.5g/cc.
In addition, another conductive paste drying film that the present invention relates to is characterized in that, prints above-mentioned conductive paste, and the maximum rising height that carries out dry resulting desciccator diaphragm is below 1.0 μ m.
In addition; The conductive paste roasting film that the present invention relates to; It is characterized in that, this conductive paste on the dielectric raw cook, print, the thickness of dry, the resulting conductive paste electrode film of roasting is at 0.8～1.0 μ m, the nickel active electrode area of this electrode film is more than 50%.
In addition; The multilayer ceramic capacitor that the present invention relates to; Above-mentioned conductive paste on the dielectric raw cook, print, dry, the resulting conductive paste electrode film of roasting thickness is at 0.8～1.0 μ m; The nickel active electrode area of this electrode film is more than 50%, and the thickness of the dielectric layer that the roasting of above-mentioned dielectric raw cook obtains is below 2 μ m.
More than; According to the present invention; Can realize to be formed on maximum rising height in the desciccator diaphragm that internal electrode sticks with paste with electroconductive nickel below 1.0 μ m, and below the roasting thickness 1.0 μ m, its multilayer ceramic capacitor is stuck with paste and adopted to the electroconductive nickel of the electrode film that densification and continuity are good.
Embodiment
The internal electrode of multilayer ceramic capacitor of the present invention forms and uses conductive paste, it is characterized in that, it is the paste that nickel powder and ceramic powders are disperseed.
[nickel powder]
In the present invention, the electrode film of dense thin stratification after, the roasting can corresponding rising height low in order to obtain is so the average grain diameter of hoping nickel powder less than 0.2 μ m, more hopes to adopt 0.1 μ m above and less than the micropowder of 0.2 μ m.When the particle diameter of nickel powder during greater than 0.2 μ m, following maximum rising height surpasses 1.0 μ m persons to be increased, and is not preferred.In more detail, nickel powder generates big particle owing to cohesion sometimes, and when the particle diameter of nickel powder during greater than 0.2 μ m, the particle diameter of big particle (D100) is greater than 1.3 μ m, and its existence goes far towards the generation of jut.
Therefore, when maximum rising height surpassed 1.0 μ m, during MLCC below making dielectric bed thickness 1.0 μ m, short circuit between electrodes made the reductions such as reliability or product percent of pass of capacitor.
Here, the nickel powder particle diameter among the present invention as long as do not do statement in advance, just is based on the particle diameter that the BET method is calculated specific area.Calculating formula is following:
Particle diameter=6/S.A * ρ (ρ=8.9 (real density of Ni), the specific area of S.A=Ni powder).
In addition, the reason that the nickel powder particle diameter is defined as less than 0.2 μ m is that this is that the electrode film of 50% above active electrode area is necessary because formation roasting thickness is 0.8～1.0 μ m.As to adopt the nickel powder of particle diameter greater than 0.2 μ m; Form the electrode film that the roasting thickness reaches 0.8～1.0 μ m; To the particle diameter of nickel powder, essential attenuate desciccator diaphragm, the filling of nickel powder particle is insufficient in desciccator diaphragm; Can not guarantee desirable desciccator diaphragm density, the result can not guarantee the active electrode area of electrode film.That is, when the particle diameter of nickel powder during greater than 0.2 μ m, electrode film breaks, and the capacity of MLCC is reduced.Also have, be described below about the active electrode area.
Further, nickel powder is spherical for being similar to, and shows that sharp-pointed particle size distribution is preferred.The granularity of nickel powder can adopt known granularity resolver (for example, registered trade mark " マ イ Network ロ ト ラ Star Network ") to measure.So-called sharp-pointed particle size distribution, the D100 that means nickel powder is preferred below 1.3 μ m, more preferably below the 1.1 μ m.As D100 during greater than 1.3 μ m, maximum rising height surpasses 1.0 μ m, aspect thin layerization, has problems as stated.Here, so-called D100 is the maximum particle size in the particle size distribution.Therefore, regulation D100's the reasons are as follows.The desciccator diaphragm of conductive paste is that nickel powder and ceramic powder pile up and form.Cooperating D100 like the bottommost at desciccator diaphragm is the big particle of 1.3 μ m, and the head portion of this particle is in the state that runs through the desciccator diaphragm surface, and then the height of projection does not have above-mentioned problem.Yet, in the time of near this big particle is configured in the desciccator diaphragm top layer, produce the problem of projection.
In the present invention, the manufacturing approach of used nickel powder is not done special qualification, for example, can suitably select to use with reducing agent reduced nickel saline solution, the liquid phase reduction that nickel powder is separated out; The gas phase reduction process that chloride vapour is directly separated out from gas phase in hydrogen; (for example, more than 600 ℃) the nickel aqueous solution of spraying makes the spray pyrolysis of its pyrolysis etc. in high temperature.
Here, carbon containing sometimes in the nickel powder.But carbon containing does not consider it is desirable from the original characteristic of nickel powder (for example, agglutinating property) yet.
For example; Adopt reducing agent reduced nickel saline solution; The liquid phase reduction that nickel powder is separated out in order to control resulting powder diameter, to prevent purpose such as cohesion, adds organic dispersing agent such as surfactant and synthesizes in reaction solution; But the organic substance that add this moment is residual in the inner grain boundary of the nickel powder that generates through reaction sometimes.
Therefore, organic dispersing agent additions such as the surfactant in the reaction solution have very big influence to the phosphorus content in the nickel powder.
In addition, adopt the pyrolysis of carbonyl nickel salt, the reduction of nickel alkoxide, the reduction of nickel chloride etc. to make the vapor phase method of nickel powders, carbon that contains in the initiation material and the impurity that becomes the carbon cause influence the phosphorus content in the nickel powder greatly.
In addition, even other different nickel powder manufacturing approaches of principle, the phosphorus content in the nickel powder of production is also different.
From the above, the present invention finds, uses outside the original management object through selection, and the low-down nickel powder of carbon component content mass ratio in the nickel powder can be made high-quality paste.
Also have, the phosphorus content analysis in the nickel powder can adopt high-frequency combustion infrared absorption spectroscopy (analyzer is the EC-12 of LECO manufacturing or the EMIA-U511 that make the hole field) to measure.
Here, the content mass ratio of carbon component in the nickel powder hopes more to hope below 0.04% below 0.06%.When the carbon component content mass ratio in the nickel powder greater than 0.06% the time owing to reduce relevantly, be unfavorable with the density of desciccator diaphragm.In addition; The reason that carbon component content mass ratio in the nickel powder is relevant with the density of desciccator diaphragm is not quite clear; But the carbon component content mass ratio in the nickel powder is as below 0.06%; Can realize the density of desirable desciccator diaphragm, the result is with desirable thickness, formation can guarantee hope the electrode film of active electrode area.On the other hand; When the carbon component content mass ratio in the nickel powder surpasses 0.06%, carbon excess residual in the electrode film, with the electrical characteristics of this residual carbon after (for example as the roasting of reason; Electrostatic capacitance amount, dielectric loss, insulation breakdown voltage etc.) worsen, be unfavorable.
[ceramic powders]
In the present invention, be added into the ceramic powders in the conductive paste, usually can be from BaTiO as perofskite type oxide
3Deng, or after wherein adding various additives, select.In addition, be preferred with the ceramic powders same composition or the similar composition that use with the principal component of dielectric layer raw cook as MLCC.
In the present invention, the particle diameter of ceramic powders is hoped less than 0.1 μ m, more hopes 0.06 μ m～0.02 μ m.When the particle diameter of ceramic powders during greater than 0.1 μ m, the particle diameter and the above-mentioned nickel powder big particle of the big particle that cohesion generates can not be ignored equally, are not preferred.
In addition, when the particle diameter of ceramic powders during greater than 0.1 μ m, desciccator diaphragm density reduces.In desciccator diaphragm; Roughly spherical nickel powder particle piles up in the gap of formation and is filled with ceramic powders; When this ceramic powders particle diameter during, can not take in the roughly spherical nickel powder particle gap, because the existence of ceramic powders greater than 0.1 μ m; Hinder the filling of nickel powder particle, the result produces the problem that can't obtain desirable desciccator diaphragm density.
In addition, when the particle diameter of ceramic powders during greater than 0.1 μ m, because above-mentioned desciccator diaphragm density reduces or the cohesion powder of ceramic powders; Maximum rising height is reached more than the 1.0 μ m; When carrying out the thin layer of dielectric layer, produce insulation resistance reduction, short circuit ratio rising etc., its result; The generation product percent of pass reduces, problems such as reliability deterioration.
The particle diameter of ceramic powders is influential to the delamination of conductive paste.When ceramic powders particle diameter during greater than 0.1 μ m, the sintering behavior of the nickel powder control difficulty that becomes, the result is that the delamination problems of electrode film takes place.
In the present invention, because the nickel powder particle grain size less than 0.2 μ m, is compared greater than the conductive paste of the nickel powder of 0.2 μ m with original particle diameter, be prone to take place delamination.In order to control nickel powder delamination of the present invention, the particle diameter of ceramic powders is necessary less than 0.1 μ m.
The containing ratio of ceramic powders hopes to reach 10～30 mass parts to metal dust 100 mass parts.More hope metal dust 100 mass parts are reached 15～25 mass parts.When the containing ratio of ceramic powders is lower than 10 mass parts, for example, can not control the sintering of Ni powder, the mismatch that the sintering of interior electrode layer and dielectric layer shrinks behavior becomes remarkable.On the other hand, when the containing ratio of ceramic powders during greater than 30 mass parts, for example, because electrode layer is to the diffusion of dielectric layer internally, the thickness swelling of dielectric layer brings harmful effect to the electrical characteristics such as reduction of dielectric constant.
[conductive paste]
The organic solvent dissolution resinous principle of conductive paste; Be to have the composition that makes inorganic constituents stable dispersion functions in paste such as conductive metal powder simultaneously; When the raw cook of electronic unit and the first-class coating of circuit substrate (printing); These powder are evenly extended, must make its loss in atmosphere before the roasting.
Here; As the organic solvent among the present invention, can use terpineol (α, β, γ and these mixture), dihydro-terpineol, octanol, decyl alcohol, three decyl alcohol, Dibutyl phthalate, butyl acetate, BC, butyl carbitol acetate, DPG monomethyl ether etc.In addition, in order to adjust viscosity, can use aromatic hydrocarbon or aliphatic hydrocarbon as the diluent of sticking with paste.For example, aliphatic hydrocarbons such as decane, nonane, heptane, the aliphatic category higher alcohol that 190～350 ℃ of preferred carbon numbers of fusing point are 8～20, for example, decyl alcohol, octanol etc., or aromatic hydrocarbon for example benzene, toluene etc. both can use separately also and can and use.This diluent is the rate of drying of sticking with paste after printing in order to regulate, or gives the viscosity characteristics of sticking with paste appropriateness and use.
As the binder resin among the present invention, can enumerate organic resins such as methylcellulose, ethyl cellulose, NC Nitroncellulose, acrylic acid, polyvinyl butyral resin, can be from wherein selecting more than a kind.Molecular weight is not done special qualification, as long as can be dissolved in above-mentioned solvent.The resin of the molecular weight of general employing 20000～200000.Also have, the amount of resin in the paste hopes to reach 1.0～5.0 quality %, and it is preferred particularly reaching 2.0～4.0 quality %.When being lower than 1.0 quality %, be difficult to obtain being suitable for the viscosity of silk screen printing, when greater than 5.0 quality %, when the unsticking mixture, residual carbon amount increases, and causes the delamination of stacked die, is unfavorable.
In conductive paste of the present invention, can add known additive in the conductive pastes such as antifoaming agent, dispersant, plasticizer, surfactant, tackifier as required.
The manufacturing that conduction is stuck with paste can be adopted known method such as 3 roller mills, ball mill.
The printing (coating) of sticking with paste can adopt known silk screen printing to carry out.
[desciccator diaphragm]
Usually, adopt conductive paste silk screen printing to be coated on the raw cook etc., for example, carry out heat drying, remove and desolvate, form the internal electrode paste drying film of predetermined pattern.At this moment, through the thickness of change silk-screen patterns, make the thickness of the conductive paste film of regulation.
In the present invention, more than the preferred 5.5g/cc of desciccator diaphragm density of conductive paste.Also have, hope that desciccator diaphragm density is high, but must not surpass the real density of metallic nickel.When desciccator diaphragm density is lower than 5.5g/cc, can not get fine and close electrode film during roasting, problem such as the generation capacity is damaged.
Also have, the assay method of desciccator diaphragm density for example, can adopt following method to measure.Stick with paste Ni and on the PET film, print, make that thickness reaches 30 μ m on 5 * 10cm area, then, in 120 ℃ air drying 40 minutes.Be cut into 1 * 1cm to dry Ni paste drying film, measure thickness and quality, calculate desciccator diaphragm density.
The mensuration of desciccator diaphragm density is behind printing conductive property paste on the PET film, to carry out, even but conductive paste of the present invention be printed on the dielectric layer raw cook and also can bring into play same characteristic, this is self-evident.
Here, so-called desciccator diaphragm density is to make the dried density of conductive paste.
In the present invention, maximum rising height hopes below 1.0 μ m, more to hope below 0.8 μ m.Its reason is, when maximum rising height during greater than 1.0 μ m, when carrying out the thin layer of dielectric layer, produces the reduction, short circuit ratio rising of insulation resistance etc., its result, and product percent of pass takes place to be reduced, problems such as reliability deterioration.When maximum rising height during, produce the problem that runs through dielectric layer and be short-circuited greater than 1.0 μ m.
Also have, the assay method of maximum rising height for example has following method.Adopt spreader (gap thickness 5 μ m), after coating Ni sticks with paste on the glass substrate, in 120 ℃ air drying 5 minutes, obtain the desciccator diaphragm of the about 3 μ m of thickness.Then, desciccator diaphragm is adopted optical means, promptly the phase shift interference mode is measured the projection on surface.Concrete is that the light from the light source that is limited to particular wavelength region, irradiation sample and reference mirror are observed surface state through the Light Interference Streaks of irradiation sample and reference mirror.Further specify is exactly to make sample every mobile on the direction of illumination of 1/4 wavelength at light, from Light Interference Streaks observation surface state.For example, (WYCO makes, and NT-1100), measures the maximum rising height of desciccator diaphragm can to adopt the light interference type surface-profile measuring instrument.
The mensuration of maximum rising height is that coating conductive paste of the present invention carries out on glass substrate, and still, even printing conductive paste of the present invention also can be brought into play same characteristic on the dielectric layer raw cook, this is self-evident.
Here, so-called maximum rising height is not to measure the maximum of the rising height of contour curve in the area and the maximum sum of the lowest point degree of depth arbitrarily, i.e. Rmax value, but the maximum of contour curve rising height in the area is measured in expression arbitrarily.
[electrode film]
Overlapping the raw cook that has formed conductive paste drying film with the sheet number of regulation; The pressurization lamination; After being cut into the shape of regulation; In inert atmosphere or contain in the inert atmosphere of a little oxygen and carry out the unsticking mixture, the high temperature in 1100～1300 ℃ in reducing atmosphere carries out roasting, makes internal electrode and dielectric sintering simultaneously.
In the present invention, when the roasting thickness of electrode film reached 0.8～1.0 μ m, it was preferred that nickel active electrode area reaches more than 50%, more preferably more than 55%.
When the roasting thickness was lower than 0.8 μ m, the continuity variation of electrode film can not be guaranteed the desirable electrical characteristics of MLCC (capacity, insulation breakdown voltage etc.), in addition, made the reduction such as reliability or product percent of pass of MLCC.On the other hand, when thickness during, can not adapt to the requirement of the small-sized high capacity of MLCC greater than 1.0 μ m.Therefore, for the MLCC that makes small-sized high capacity realizes keeping desirable characteristic or reliability, the thickness of electrode film should reach 0.8～1.0 μ m.
The active electrode area is lower than at 50% o'clock, can not guarantee the continuity of electrode film, can not guarantee the desirable electrical characteristics of MLCC (electrostatic capacitance amount, insulation breakdown voltage etc.), in addition, makes the reduction such as reliability or product percent of pass of MLCC.
Also have, the assay method of nickel active electrode area for example has following method.Adopt silk screen printing, on aluminum oxide substrate, print, make the roasting thickness reach 0.8 μ m, after the drying, the electrode film after roasting under the inert atmosphere is carried out image analysis, be nickel active electrode area to likening to of nickel area coverage.
Specifically, image analysis for being easy to use computer Recognition to the image that obtains with the observation by light microscope electrode film, and has the image processing of emphasical contrast and the mensuration of the nickel area coverage in the visual field, the device of parsing.For example, through adopting LUZEX (registered trade mark) image processing resolution system, can obtain the nickel effective area of conducting film of the present invention.
Also have, the evaluation of nickel active electrode area, printing conductive property paste carries out on aluminum oxide substrate, and printing on above-mentioned dielectric layer raw cook, dry, roasting can certainly be brought into play the desirable characteristic of conductive paste.
Here, so-called active electrode area is the area coverage rate that forms the nickel (metal) of electrode in the electrode film after the conductive paste printing that is used to form electrode film, drying, the roasting.
Embodiment and comparative example
Below; Based on embodiment, comparative example; To the data (table 2) of the influence of quality, be elaborated together when the data (table 1) of the influence of quality being changed with the content mass ratio of confirming to make carbon component in the nickel by powder when confirming various nickel powder particle diameters and ceramic powders mechanical fraction.Also have,, the technical scope of putting down in writing in claims of the present invention is not done any qualification through embodiments of the invention.
Conductive paste is made with 3 roller machines, as the evaluation of the desciccator diaphragm of this paste, measures the density and the maximum rising height of desciccator diaphragm; As the evaluation of roasting film, measure the active electrode area; As the electrical characteristics evaluation, measure the short circuit ratio of multilayer ceramic capacitor, its result is shown in table 1.
The manufacturing of (1) sticking with paste
The composition of sticking with paste: Ni powder (particle diameter=0.4 μ m, 0.2 μ m, 0.17 μ m, 0.13 μ m) 47 quality %, ceramic powder (particle diameter=0.2 μ m, 0.1 μ m, 0.08 μ m, 0.05 μ m, 0.02 μ m) 10.8 quality %, carrier A 42.2 quality %.Carrier A:,, heat (60 ℃) and process carrier as the terpineol 91 quality % of organic solvent ethyl cellulose (molecular weight 70000) 9 quality % as resinous principle.Nickel powder is used the liquid-phase reduction manufactured, makes organic dispersing agent amounts such as the surfactant increase and decrease that is added in the reaction solution, from the nickel powder of the various carbon contents that obtain, selects the content mass ratio of the carbon component in the Ni powder to reach 0.04% and 0.06% sample.
(2) manufacturing of multilayer ceramic capacitor
Adopt the conductive paste of above-mentioned manufacturing to make MLCC, estimate short circuit ratio as electrical characteristics.Evaluation assessment is introduced below.
(3) mensuration of maximum rising height
Adopt spreader (gap thickness 5 μ m), after coating Ni sticks with paste on the glass substrate, in air,, obtain the desciccator diaphragm of the about 3 μ m of thickness in 120 ℃ of dryings 5 minutes.Then, desciccator diaphragm is adopted optical means, (WYCO makes, and NT-1100), measures the maximum rising height of desciccator diaphragm with the light interference type surface-profile measuring instrument.Measuring number is 3 places, wherein the highest rising height as maximum rising height.
(4) desciccator diaphragm density measurement
Desciccator diaphragm density measurement is imprinted on paste and makes its area that reaches 5 * 10cm on the PET film, behind the thickness 30 μ m, in air in 120 ℃ of dryings 40 minutes.Be cut into 1 * 1cm to dry Ni paste drying film, measure thickness and quality, calculate desciccator diaphragm density.Measuring number is 30 places, and the mean value of resulting film density is as the film density of this conductive paste.
Desciccator diaphragm density=(quality of sample)/(area * thickness of sample)
(5) active electrode area
Be imprinted on paste with silk screen print method and make the roasting thickness reach 0.8 μ m on the aluminum oxide substrate, after the drying, measure the area coverage ratio of nickel to the electrode film after roasting under the inert atmosphere with image analysis apparatus (LUZEX III), as the active electrode area.
(6) manufacturing of lamination MLCC
Adopt the conductive paste of above-mentioned manufacturing to make MLCC, estimate short circuit ratio as electrical characteristics.Evaluation assessment is described below.
Printing conductive property paste on the original dielectric raw cook of thickness 3.0 μ m, dry back be 10 plies, and the chip of 3.2 * 1.6mm size is processed in pressurized adhesion, cut-out.Behind this chip unsticking mixture, under weak reducing atmosphere in 1240 ℃ of roastings.On chip, be coated with terminal electrode after the roasting, process 20 of multilayer ceramic capacitors.With the poor short circuit generation number of this multilayer ceramic capacitor of Q table mensuration, obtain bad incidence.Short circuit ratio must be below 5%.Also have, the internal electrode thickness after the chip roasting is 0.8 μ m, and the dielectric bed thickness is 2.0 μ m.
Table 1
(notes) short circuit ratios "-", expression roasting film evaluation result is bad, does not carry out the electrical characteristics evaluation.
Can know that from the evaluation result of the embodiment 1 of table 1 record show that desciccator diaphragm density is that the nickel of 5.7g/cc is stuck with paste, maximum rising height is below 1.0 μ m, the active electrode area is 55%, presents the good result of no short circuit.On the other hand, like comparative example 1, shown in 2, can know that short circuit ratio is up to 60% when maximum rising height during greater than 1.0 μ m; When the thick 1.0 μ m of electrode are following, can not guarantee densification and keep successional electrode.And can know that this maximum rising height, desciccator diaphragm density depend on Ni powder footpath, BaTiO greatly
3Carbon component content mass ratio in powder footpath, the Ni powder.
Then, from the nickel powder that adopts the liquid-phase reduction manufactured, carbon component content mass ratio reaches 0.04%, 0.06%, 0.11%, 0.17% nickel powder in the selection Ni powder, the BaTiO by any nickel powder 47 quality %, particle diameter 0.05 μ m
3The paste that powder 10.8 quality %, carrier A 42.2 quality % are constituted is made with 3 roller machines, obtains 4 kinds of pastes shown in the table 2.These pastes are measured with the determination method of above-mentioned desciccator diaphragm density.The result is shown in table 2.Also have, in the present embodiment, nickel powder is used the liquid-phase reduction manufactured, but is not limited to this method, uses from the nickel powder that other manufacturing approaches are made also can according to the selected nickel powder of carbon content.
Table 2
Can know from the result of the embodiment shown in the table 24,5 and the result of comparative example 4,5; Carbon component content mass ratio is below 0.06% in the Ni powder; Desciccator diaphragm density shows more than the 5.5g/cc, when carbon component content mass ratio in the Ni powder greater than 0.06% the time, desciccator diaphragm density is lower than 5.5g/cc.Therefore, carbon component content mass ratio has very big influence to desciccator diaphragm density in the Ni powder of use.
Claims (6)
1. conductive paste; It is characterized in that; At least the mass ratio that contains the carbon component content in the nickel powder below 0.06%, average grain diameter is lower than the nickel powder of 0.20 μ m; And average grain diameter is lower than the ceramic powders of 0.10 μ m, and above-mentioned relatively nickel powder 100 mass parts of the containing ratio of above-mentioned ceramic powders are 10～30 mass parts.
2. conductive paste; It is characterized in that; At least the mass ratio that contains the carbon component content in the nickel powder below 0.06%, average grain diameter is lower than the nickel powder of 0.20 μ m; Average grain diameter is lower than the ceramic powders of 0.10 μ m, and binder resin and organic solvent, and above-mentioned relatively nickel powder 100 mass parts of the containing ratio of above-mentioned ceramic powders are 10～30 mass parts.
3. a conductive paste drying film is characterized in that, printing claim 1 or 2 described conductive pastes, and the desciccator diaphragm density of carrying out dry resulting desciccator diaphragm is more than 5.5g/cc.
4. a conductive paste drying film is characterized in that, printing claim 1 or 2 described conductive pastes, and the maximum rising height that carries out dry resulting desciccator diaphragm is below 1.0 μ m.
5. conductive paste roasting film; It is characterized in that; Claim 1 or 2 described conductive pastes on the dielectric raw cook, print, thickness dry, the resulting conductive paste electrode film of roasting is 0.8～1.0 μ m, the nickel active electrode area of this electrode film is more than 50%.
6. multilayer ceramic capacitor; It is characterized in that; Claim 1 or 2 described conductive pastes on the dielectric raw cook, print, thickness dry, the resulting conductive paste electrode film of roasting is 0.8～1.0 μ m; The nickel active electrode area of this electrode film is more than 50%, and the thickness of the dielectric layer that the roasting of above-mentioned dielectric raw cook obtains is below 2 μ m.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2007-118040 | 2007-04-27 | ||
| JP2007118040A JP4947418B2 (en) | 2007-04-27 | 2007-04-27 | Conductive paste, conductive paste dry film, and multilayer ceramic capacitor using the same |
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| CN101295582A CN101295582A (en) | 2008-10-29 |
| CN101295582B true CN101295582B (en) | 2012-10-24 |
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| JP (1) | JP4947418B2 (en) |
| CN (1) | CN101295582B (en) |
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| KR20120066942A (en) * | 2010-12-15 | 2012-06-25 | 삼성전기주식회사 | Conductive paste composition for inner electrode, multilayer ceramic capacitor using the same and a manufacturing method thereof |
| KR101580350B1 (en) | 2012-06-04 | 2015-12-23 | 삼성전기주식회사 | Multilayered ceramic elements |
| KR101548787B1 (en) | 2012-06-05 | 2015-08-31 | 삼성전기주식회사 | Multilayered ceramic elements |
| WO2015040916A1 (en) * | 2013-09-17 | 2015-03-26 | 株式会社村田製作所 | Electroconductive paste and ceramic electronic component |
| JP6613551B2 (en) * | 2014-07-31 | 2019-12-04 | 住友金属鉱山株式会社 | Multilayer ceramic capacitor internal electrode paste and multilayer ceramic capacitor |
| KR20240049855A (en) * | 2018-01-30 | 2024-04-17 | 테크나 플라즈마 시스템 인코포레이티드 | Metallic Powders for Use as Electrode Material in Multilayer Ceramic Capacitors and Method of Manufacturing and of Using Same |
| JP7290914B2 (en) * | 2018-02-26 | 2023-06-14 | 太陽誘電株式会社 | Manufacturing method of multilayer ceramic capacitor |
| KR20210109531A (en) * | 2019-01-08 | 2021-09-06 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Nickel paste for multilayer ceramic capacitors |
| CN114920556B (en) * | 2022-06-09 | 2022-11-29 | 潮州三环（集团）股份有限公司 | Ceramic slurry and multilayer ceramic capacitor prepared from same |
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| JP4552260B2 (en) * | 2000-03-30 | 2010-09-29 | Ｔｄｋ株式会社 | Nickel powder, electrode paste, and electronic component manufacturing method |
| JP2005071714A (en) * | 2003-08-21 | 2005-03-17 | Murata Mfg Co Ltd | Conductive paste and laminated ceramic electronic component |
| JP2005203213A (en) * | 2004-01-15 | 2005-07-28 | Matsushita Electric Ind Co Ltd | Conductive paste and laminated ceramic electronic component using it |
| TWI399254B (en) * | 2004-12-10 | 2013-06-21 | Mitsui Mining & Smelting Co | Nickel powder and its manufacturing method and conductive paste |
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| JP特开2000-150293A 2000.05.30 |
| JP特开2005-79504A 2005.03.24 |
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| Publication number | Publication date |
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| CN101295582A (en) | 2008-10-29 |
| TW200915351A (en) | 2009-04-01 |
| TWI374454B (en) | 2012-10-11 |
| JP4947418B2 (en) | 2012-06-06 |
| JP2008277066A (en) | 2008-11-13 |
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