CN1581388A - Multi-layer ceramic capacitor and its preparing method - Google Patents

Abstract

X7R sheet type multilayer ceramic capacitor includes inner electrode, laminated dielectric layer crossed with inner electrode, and terminal electrode connected to out end of the inner electrode. Main components of the dielectric layer is composite oxides of Ba, Ti, and the dielectric layer also includes minor constituents from one or more following oxides: Ca, Si, Mn, Y, Zr, Zn, Ni, Nb. Metal nickel is utilized for inner electrode. The invention prepares laminar ceramic capacitor in large capacity and number of layers, and lowered production cost.

Description

Multilayer ceramic capacitor and preparation method thereof

Technical field

The present invention relates to a kind of ceramic capacitor and manufacture method thereof, more particularly, the present invention relates to a kind of with nickel or nickel alloy as X7R multiple-layer sheet ceramic capacitor of interior electrode and preparation method thereof.

Background technology

Chip multilayer ceramic capacitor (MLCC) is a kind of new electronic component, is used for the surface mount of consumer electronics complete machines such as communication, computer, household electrical appliance in a large number.Along with global rapid development of surface mount, the output of surface mount component rises rapidly, and the MLCC demand constantly rises.And X7R type MLCC constantly develops to miniaturization, low cost, high capacity, high reliability direction, to satisfy the requirement that these electronic equipments constantly develop to microminiaturization, thin layerization, high performance.Simultaneously because characteristics such as the high specific volume of X7R type MLCC, high performance-price ratio, high reliability, it just progressively replaces part aluminium electrolytic capacitor, tantalum electrolytic capacitor and film capacitor.

At present, it is interior electrode that X7R type multilayer sheet type ceramic capacitor (MLCC) extensively adopts precious metals ag/Pd material, for the high product of some quality requirements even adopt electrode in the full Pd, termination electrode then is Ag or AgO, adopts the expensive advantage that mainly contains the following aspects as interior electrode that belongs to more:

At first, because inside and outside electrode all adopts inactive noble metal to make, binder removal, sintering and burning end process can be carried out in air, and the ceramic dielectric system of use does not need to have resistance to reduction, so raw-material making is simple relatively;

Secondly, because binder removal carries out in air, oxygen content is abundant, so can finish the binder removal process at lower temperature with in than the short time, operating efficiency is higher relatively, and energy resource consumption is relatively low.

But there are many deficiencies in the MLCC product of Ag/Pd system, mainly shows following several respects:

At first, production cost is higher, owing to adopt precious metals pd/interior electrode of Ag work and precious metals ag to make termination electrode, causes higher production cost;

Secondly, reliability of products can poor, and owing to burning system in the employing of Ag/Pd system X7R type MLCC product, it is more to make that product burns till the posterior spiracle rate, and the product internal flaw is more, and product quality is under some influence;

Once more, be difficult to realize high capacity, burn the porcelain powder of system during Ag/Pd system X7R type MLCC product adopts, medium is difficult to realize filming, and the decreasing insulating of product is difficult to realize high number of plies double exposure simultaneously, is prone to layering after burning till.

Summary of the invention

The present invention is directed to above-mentioned the deficiencies in the prior art, a kind of X7R chip multilayer ceramic capacitor is provided, this capacitor can adopt nickel or nickel alloy as interior electrode, has reduced production cost, and has had excellent dielectric properties.

Chip multilayer ceramic capacitor of the present invention comprises: interior electrode, with dielectric layer interior electrode crossing lamination, that make by the dielectric ceramic material powder and the termination electrode that is connected with the interior electrode of deriving, the number of plies of dielectric layer is the 20-500 layer, thickness is 2-20 μ m after the burning of every layer of dielectric layer, in every layer after the burning of electrode thickness be 0.5-2.0 μ m.

The dielectric ceramic material powder that is used for preparing dielectric layer among the present invention comprises key component and accessory constituent, wherein:

The chemical constitution formula of key component is Ba _1-x-ySr _xCa _yTiO ₃, in the formula, 0.05≤x≤0.4,0.01≤y≤0.25;

Accessory constituent comprises first accessory constituent and second accessory constituent again, wherein:

First accessory constituent is: α Y ₂O ₃+ β MgO+ (1-alpha-beta) MnO, in the formula, α, β represent mol ratio, its scope is 0.2≤α≤0.8,0.1≤β≤0.6;

Second accessory constituent is SiO ₂-TiO ₂-Al ₂O ₃

And for key component weight, the weight percentage of first accessory constituent is 0.2wt.%～2.0wt.%; The weight percentage of second accessory constituent is 0.2wt.%～5.0wt.%.

Key component Ba for the dielectric ceramic powder _1-x-ySr _xCa _yTiO ₃, when y＜0.01, sample forms semiconductor; On the other hand, and work as y＞0.25, sample is densified sintering product fully.So limit 0.01≤y≤0.25.When x＜0.05, the average life span of sample is short; And when x＞0.4, the insulation resistance of sample is low.So limit 0.05≤x≤0.4.

The first accessory constituent α Y for the dielectric ceramic powder ₂O ₃+ β MgO+ (1-alpha-beta) MnO, when α, β exceeded 0.2≤α≤0.8,0.1≤β≤0.6 scope, the volume change rate of sample exceeded the EIA-X7R standard.

When relative weight part mm of first accessory constituent＜0.2, sample is sintering fully; And when m＞2.0, the volume change rate of sample exceeds the EIA-X7R standard.So limit 0.2≤m≤2.0.

When wanting for the second time component S iO ₂-TiO ₂-Al ₂O ₃Relative weight part n＜0.2 o'clock, sample is sintering fully; And when n＞5.0, the volume change rate of sample exceeds the EIA-X7R standard.So limit 0.2≤n≤5.0.

Wanting for the second time component S iO ₂-TiO ₂-Al ₂O ₃In, the mol ratio of each oxide is preferably:

SiO ₂∶TiO ₂∶Al ₂O ₃＝0.2-1.8∶0.2-1.8∶0.2-1.8。

In above-mentioned ceramic capacitor, interior electrode and termination electrode are preferably made by base metal, and more preferably: interior electrode is made by nickel or nickel alloy, and termination electrode is made by copper or copper alloy.

Among the present invention, it is that the nickel slurry printing of 0.1-0.4 μ m is made that interior electrode can adopt the nickel powder granularity, and the nickel of electrode heavily is 5.0-7.0 milligram/square inch in the gained.Can also be added with BaTiO in the above-mentioned nickel powder ₃Ceramic powder, its ratio is between 100/13-100/25.

On the other hand, the invention provides a kind of preparation method of chip multilayer ceramic capacitor, this method is suitable for the preparation of the high number of plies, thin layerization, big capacity chip multilayer ceramic capacitor.This method comprises: mix slurry, make the medium diaphragm, replace electrode and dielectric layer, lamination, cutting, binder removal, sintering, end-blocking electrode in the double exposure, burn end, nickel plating and zinc-plated operation, wherein, above-mentioned binder removal operation is at N ₂Carry out under the protection of atmosphere; Above-mentioned sintering circuit is divided into heat up section, the high temperature section of burning till and temper section, and wherein, heat up section and the high temperature section of burning till are to contain H ₂N ₂Carry out H under the atmosphere protection ₂Content is controlled at the 0.05-5% of atmosphere total amount, and the sintering temperature of the high temperature section of burning till is controlled at 1200 ℃-1400 ℃, and the temper section is the N in oxidizability ₂Carry out in the atmosphere, wherein, O ₂Content is 10ppm-100ppm, and the temperature of temper section is 800 ℃-1050 ℃.

Preferably, O in the temper section ₂Content be 30ppm-80ppm.

In said method, burning the end operation is to contain O ₂N ₂Segmentation is carried out in the atmosphere, wherein, is the low-temperature zone of described burning end operation below 500 ℃, and 500 ℃ is the high temperature section of described burning end operation to burning the end maximum temperature, and burning the end maximum temperature is 700 ℃-1050 ℃, and N in the low-temperature zone ₂Oxygen content in the atmosphere will be higher than the N of high temperature section ₂Oxygen content in the atmosphere, low-temperature zone N ₂Oxygen content in the atmosphere is 50-400ppm, high temperature section N ₂Oxygen content in the atmosphere is 0-50ppm.

Preferably, burning the end maximum temperature is 800 ℃-950 ℃, N in the low-temperature zone ₂Oxygen content in the atmosphere is 100-300ppm, N in the high temperature section ₂Oxygen content in the atmosphere is 0-30ppm.

Dielectric layer of the present invention has fine structure owing to adopted the resistance to reduction porcelain, the less and good stability of its particle behind the sintering, and the space seldom has good insulation property and high-dielectric coefficient in the ceramic dielectric layer.This ceramic powder is adding H ₂Reducing atmosphere under carry out sintering, serious oxygen loss can not take place in ceramic body, the oxygen room can not occur and causes the shortcoming such as insulation (IR) decline, loss (DF) rising of MLCC.

In the present invention, interior electrode adopts base metal nickel to make, and termination electrode adopts Cu to make.With adopting Pd/Ag is that the MLCC product of interior electrode is compared, and during electrode, its rupture strength is bigger in making of Ni, and this helps resisting the mechanical stress effect when assembling and matrix cutting.Its termination electrode is metal Cu in addition, and Ni is adjacent with the Cu atomic number, and atomic radius is close, the two easier being combined into one when burning end, and it is good to make that internal and external electrode connects, thereby guarantees that product has good reliability.

The obtained chip multilayer ceramic capacitor of the present invention, the used prices of raw and semifnished materials are low, and especially the electrode size price is about 1/10 of Ag/Pd approximately, and this just greatly reduces production cost; Simultaneously good according to these properties of product of producing, the quality height, and realized the high number of plies, miniaturization and jumbo requirement.

Description of drawings

Fig. 1 is preparation technology's flow chart of chip multilayer ceramic capacitor;

Fig. 2 is the section of structure of X7R chip multilayer ceramic capacitor.

Among the figure, the implication of each Reference numeral is:

Electrode in 1

2 dielectric layers

3 termination electrodes

4 nickel dams

5 tin layers

Embodiment

The preparation of A, dielectric ceramic material powder

At first, making purity is 99 or higher BaCO ₃, CaCO ₃, SrCO ₃And TiO ₂As raw material;

Then, with BaCO ₃, CaCO ₃, SrCO ₃And TiO ₂Powder weighing also mixes, and obtains with general formula

Ba _1-x-ySr _xCa _yTiO ₃

The raw material of the key component of expression, x, y list in the table 6 in the general formula.Place ball mill to carry out wet-milling in this mixture, the temperature with 1000～1200 ℃ was calcined 1～3 hour in air subsequently, thereby obtained the key component powder after the calcining.

Take by weighing SiO ₂, TiO ₂, Al ₂O ₃Powder, and press 0.2-1.8: the mixed in molar ratio of 0.2-1.8: 0.2-1.8.Place ball mill to carry out wet-milling in this mixture, the temperature with 400～1000 ℃ was calcined 1～3 hour in air subsequently, thereby wanted component powders the second time after obtaining to calcine.

With the key component powder after the calcining, the Y in first accessory constituent ₂O ₃, Mg (OH) ₂, MnCO ₃Weighing and mix in second accessory constituent after powder and the calcining.Wherein, contain first accessory constituent of m weight portion and second accessory constituent of n weight portion with respect to the key component of per 100 weight portions; First accessory constituent is with general formula

αY ₂O ₃+βMgO+(1-α-β)MnO

Expression (seeing Table 6).Place ball mill to carry out wet-milling said mixture, dry in 100～150 ℃ temperature subsequently, thus obtain dried dielectric ceramic material powder.

The preparation process of B, chip multilayer ceramic capacitor:

(1) the dielectric ceramic powder is mixed with PVB (polyvinyl butyral resin), be assigned in other additives again, adopt dispersion machine fully to mix, form the porcelain slurry, in dispersion process, both guaranteed the dispersion of porcelain powder, prevent again that the porcelain pruinescence is too levigate and influence properties of product;

(2) adopt the film casting technology to prepare the medium diaphragm, guarantee the inner pore-free of diaphragm, impurity, diaphragm compactness is good;

(3) adopt the printing stack technology of Roll to Roll, make the crust piece of high printing quality, high aligning accuracy;

(4) above-mentioned crust piece is carried out lamination, cuts into raw cook;

(5) sintering;

(6) chip behind the above-mentioned sintering is carried out chamfering, end-blocking, at N ₂Burn end in 700 ℃ of-1050 ℃ of temperature under the protective atmosphere;

(7) will burn nickel plating (4) and zinc-plated (5) that end back gained chip carries out two end electrodes, make described X7R matrix formula multilayer ceramic capacitor.

In said method, sintering circuit is one of most important technology during whole X7R matrix formula multilayer ceramic capacitor is made.Because electrode is a metallic nickel in of the present invention, when higher (or oxygen content) is easily oxidized and lose electrode conductivuty when heat-treating in air.Therefore electrode needs to burn till under reduction (or inertia) atmosphere.But meanwhile in the dielectric material+Ti of 4 valencys easily is reduced during sintering under reduction (or inertia) atmosphere and becomes+Ti of 3 valencys, changed ceramic crystal structure, makes ceramic dielectric become semiconductor.Therefore choosing burning till compactness, the dielectric property of back ceramic body of sintering temperature control and atmosphere curve, the capacity of product (C), insulate (IR), all there is very big influence loss (DF) and proof voltage aspects such as (BDV).

In order to make ceramic physical efficiency sintering under reducing atmosphere, when making ceramic powder, just ceramic powder has been done some adjustment, mainly be in ceramic powder, to add some anti-reducing agents (as metallic elements such as Ca, Mg or Y), strengthen the ceramic powder resistance to reduction.Except in the improvement aspect the dielectric material, the improvement of sintering process also is necessary, and the improvement of sintering process is mainly in the control with sintering curve chosen of atmosphere curve:

A. atmosphere control technology

Guarantee that at first electrode is not oxidized in heat up section and high temperature section, thus these two sections we are at N ₂The more H of middle adding ₂, H ₂Content is controlled at the 0.05-5% of atmosphere total amount, preferably is controlled at 1-3%.In order to reduce the reduction of ceramic dielectric, in guaranteeing under the not oxidized prerequisite of electrode, H ₂Content is unsuitable too high.Tempering Duan Ze is at N then ₂An amount of O of middle adding ₂, oxygen is added in the oxygen room that produces when ceramic body is reduced go, reply the dielectric property of ceramic body.

The oxidizability N of temper ₂In the atmosphere, O ₂Content is also relevant with the used porcelain of inner electrode and dielectric layer.To have listed with Ni in the table 1 be interior electrode and when adopting foregoing dielectric material, designed 10,50 respectively, the result of the oxygen content of 100ppm.

Table 1

Tested number	Tempering section oxygen content	High fever temperature	????DF(×10 -4)	????25℃，IR(Ω)
					????1	??10ppm/900℃/3Hr	??1280℃/2Hr	????188-211	????3×10 9
????2	??50ppm/900℃/3Hr	??1280℃/2Hr	????165-189	????1×10 10
					????3	??100ppm/900℃/3Hr	??1280℃/2Hr	????206-241	????1×10 10

Under the identical condition of other technology, we only regulate the oxygen content of tempering section, and difference has appearred in the properties of product that obtain, and mainly are interior electrode Ni with due to different variations has taken place under these oxygen contents ceramic body.

Under the oxygen content of test 1 10ppm, interior electrode Ni keeps metallic state, and oxidation does not take place, and the oxygen that ceramic body fails fully the front sintering stage to be lost under this condition recovers, when there is the oxygen room in ceramic body inside, and a part of Ti ⁴⁺Become Ti ³⁺, ceramic body becomes semiconductor, so the IR value of product is lower, can not reach criterion of acceptability.

When the oxygen content height is to 100ppm in test 3, oxidation has taken place and has lost electric conductivity in interior electrode part branch, the continuity variation of electrode, the connection of internal and external electrode is variation also, the DF value of product will uprise, the capacity of product also can descend and the numerical value dispersion significantly simultaneously, and cracking appears in electrode and porcelain body side in the two ends of product.The too high oxygen level of tempering section as can be seen, anodizing is serious and cause cracking.

The oxygen content of the 50ppm of test 2 is then more moderate, and electrode Ni was not oxidized in both can having guaranteed under this condition, can fully refill the oxygen that ceramic body loses at sintering stage again simultaneously, can reach best properties of product.

B. temperature control technology

In the sintering process of MLCC, there is certain difference in the shrinkage curve of interior electrode Ni and ceramic body, in order to make the shrinkage curve of the two more approaching, reaches the purpose of common burning, we have added an amount of ultrafine ceramic powder in electrode size, carry out the adjustment of sintering curre simultaneously.Burn till maximum temperature and be controlled at 1200 ℃-1400 ℃.Consistent for the contraction that guarantees nickel entoplasm and porcelain body, begin to the control of the heating rate of highest temperature section very crucially at 900-1000 ℃, major parameter is 1-5 ℃/min.

Burning end is at N ₂Carrying out under the atmosphere protection, also is one of critical process of making, and it has directly determined the success or failure of its making.To consider when burning end that Cu is not oxidized, the organic resin in the Cu end slurry will fully be got rid of at a lower temperature, the immersion depth of frit in porcelain body etc.Accomplished simultaneously above some just can obtain good, and the compact Cu of the ceramic body termination of internal structure densification, electric conductivity.

Cu end slurry mainly is made up of Cu powder, frit, organic resin and organic solvent.Wherein organic solvent is just discharged in the drying course when end-blocking basically fully, organic resin is a macromolecular material, and boiling point and decomposition temperature are all than higher, and it just need be discharged when burning end, like this, the just only Cu of remaining conduction and the vitreum used in conjunction with porcelain body in the termination of last chip.So what we will control when burning end is to add sufficient oxygen when lower temperature section (softening temperature of frit below), make that organic resin as much as possible decomposes discharge in the end slurry, just do not make generation hole in termination when having arrived the high temperature glass frits sintering.In addition, will guarantee that at high temperature Cu is not oxidized, this just requires its oxygen content low, and considers that simultaneously the oxide in the frit is not reduced, and the Control for Oxygen Content of highest temperature section is moderate.

In general, below 500 ℃ the low-temperature space that burns the end operation, at this temperature section, organic resin decomposes; 500 ℃ is the high-temperature region of burning the end operation to burning the end maximum temperature, and firing termination temperature generally is controlled at 700 ℃-1050 ℃, is preferably 800 ℃-950 ℃.N in the low-temperature space ₂Oxygen content in the atmosphere will be higher than N in the high-temperature region ₂Oxygen content in the atmosphere.Generally speaking, at low-temperature space N ₂Oxygen content in the atmosphere is 50-400ppm, is preferably 100-300ppm; At high-temperature region N ₂Oxygen content in the atmosphere is 0-50ppm, is preferably 0-30ppm.

Make X7R matrix formula multilayer ceramic capacitor in addition and run into the phenomenon that the most difficult problem is product appearance insulation decline after the life tests test of carrying out under the HTHP.Insulation resistance is being owing to occur the situation of semiconducting in the process of ceramic body at sintering easily through main reasons for decrease after the life test, the coupling sintering process from interior electrode and ceramic material in addition, also easily behind sintering inside tiny flaw appears, cause product under the condition of HTHP, to occur losing efficacy.For addressing these problems, we mainly make adjustment on aspect atmosphere of burning till and the interior electrode nickel slurry.Accurate control by atmosphere in the sintering process and to the selection of the particle size distribution and the specific area of nickel powder, nickel powder/inorganic additive ratio is adjusted and the heavy adjustment of printing nickel, and it is consistent with the porcelain film to make that the nickel slurry shrinks, and makes its electrode combine better with medium.Solve the life-span Problem of Failure of X7R product.

Table 2

Tested number	??H 2Content	Tempering section O 2Content	The basic electric property energy	Life test result
					??1	??0.5％	??30ppm	Capacity disperses	-
??2	??1.0％	??30ppm	Capacity disperses	Qualified
					??3	??1.5％	??30ppm	In the capacity set	3/200 lost efficacy
??4	??1.5％	??50ppm	In the capacity set	Qualified
					??5	??2.0％	??50ppm	In the capacity set	1/200 lost efficacy
??6	??2.0％	??100ppm	Capacity disperses	Qualified

Table 3

Tested number	Nickel powder granularity (D50)	Life test result
			????1	??0.30μm	Qualified
????2	??0.50μm	1/200 lost efficacy
			????3	??0.80μm	5/200 lost efficacy

Table 4

Tested number	Nickel powder/inorganic additive	Life test result
			????1	????100/10	Good
????2	????100/20	2/200 lost efficacy
			????3	????100/30	4/200 lost efficacy

Table 5

Tested number	Nickel is heavy	Life test result
			????1	????6.0mg/in2	Good
????2	????8.5mg/in2	1/200 lost efficacy
			????3	????10.0mg/in2	3/200 lost efficacy

Find out by the analysis of table 2-table 5, it is between the 1.0-3.0% that firing atmosphere is controlled at hydrogen content, proper between the tempering section oxygen content 30-80ppm, the making nickel powder granularity of interior electrode nickel slurry is controlled at 0.1-0.4 μ m, and nickel powder/inorganic additive proportional control is between 100/13-100/25.Interior electrode nickel slurry printing nickel heavily is controlled at 5.0-7.0mg/in2.

Embodiment 1:

Get 4000g nickel electrode X7R type dielectric material, its prescription is as shown in table 6 below:

Table 6

Sample number into spectrum	??????100g?Ba 1-x-ySr xCa yTiO 3		??????mgαY 2O 3+βMgO+(1-α-β)MnO			????ngSiO 2-TiO 2-Al 2O 3
							????x	????y	????α	????β	????m	????n
	????1*	????0.20	????0.005	????0.4	????0.5	????1.2							????0.8
????2							????0.20	????0.01	????0.4	????0.5	????1.2	????0.8
	????3	????0.20	????0.20	????0.4	????0.5	????1.2							????0.8
????4							????0.20	????0.25	????0.4	????0.5	????1.2	????0.8
	????5*	????0.20	????0.30	????0.4	????0.5	????1.2							????0.8
????6*							????0.01	????0.20	????0.4	????0.5	????1.2	????0.8
	????7	????0.05	????0.20	????0.4	????0.5	????1.2							????0.8
????8							????0.10	????0.20	????0.4	????0.5	????1.2	????0.8
	????9	????0.30	????0.20	????0.4	????0.5	????1.2							????0.8
????10							????0.40	????0.20	????0.4	????0.5	????1.2	????0.8
	????11*	????0.50	????0.20	????0.4	????0.5	????1.2							????0.8
????12*							????0.20	????0.20	????0.4	????0.5	????0.1	????0.8
	????13	????0.20	????0.20	????0.4	????0.5	????0.2							????0.8
????14							????0.20	????0.20	????0.4	????0.5	????0.5	????0.8
	????15	????0.20	????0.20	????0.4	????0.5	????0.8							????0.8
????16							????0.20	????0.20	????0.4	????0.5	????1.5	????0.8
	????17	????0.20	????0.20	????0.4	????0.5	????2.0							????0.8
????18*							????0.20	????0.20	????0.4	????0.5	????2.5	????0.8
	????19*	????0.20	????0.20	????0.4	????0.5	????3.0							????0.8
????20*							????0.20	????0.20	????0.1	????0.8	????1.2	????0.8

* with the sample of asterisk outside scope of the present invention

Table 6 (continuing)

Sample number into spectrum	100 weight portion Ba 1-x-ySr xCa yTiO 3		M weight portion α Y 2O 3+βMgO+(1-α-β)MnO			N weight portion SiO 2-TiO 2-Al 2O 3
							????x	????y	????α	????β	????m	????N
	????21*	????0.20	????0.20	????0.2	????0.7	????1.2							????0.8
????22							????0.20	????0.20	????0.3	????0.6	????1.2	????0.8
	????23	????0.20	????0.20	????0.5	????0.4	????1.2							????0.8
????24							????0.20	????0.20	????0.8	????0.1	????1.2	????0.8
	????25*	????0.20	????0.20	????0.9	????0	????1.2							????0.8
????26*							????0.20	????0.01	????0.3	????0.6	????1.2	????0.1
	????27	????0.20	????0.20	????0.5	????0.4	????1.2							????0.2
????28							????0.20	????0.25	????0.8	????0.1	????1.2	????0.4
	????29	????0.05	????0.20	????0.4	????0.5	????1.2							????0.8
????30							????0.10	????0.20	????0.4	????0.5	????1.2	????2.0
	????31	????0.30	????0.20	????0.4	????0.5	????1.2							????3.0
????32							????0.40	????0.20	????0.4	????0.5	????1.2	????4.0
	????33	????0.30	????0.20	????0.4	????0.5	????1.2							????5.0
????34*							????0.40	????0.20	????0.4	????0.5	????1.2	????6.0

Porcelain powder, plasticizer, dispersant, defoamer, toluene and the ethanol of prescription more than in ball grinder, adding, ball milling is 5 hours under the rotating speed of 85 ± 3rpm; In jar, add the binder ball milling again and made the porcelain slurry in 10 hours.Described plasticizer, dispersant, defoamer, binder are that those skilled in the art are known.

Above-mentioned porcelain slurry is become the dielectric film of 10um with film casting machine curtain coating, with Roll toRoll mode of printing, by the custom-designed 0805 specification composite wire slurry figure that on dielectric film, prints electrode, contraposition mode by the CCD scanning patter obtains clinging to piece after printing 60 layers of the dielectric film laminations of electrode again, carries out making the electric capacity green compact after lamination, the cutting.By the laggard promoting the circulation of qi atmosphere of binder removal sintering, make the ceramic crystalline grain growth, the porcelain body densification, electrode combines closely with ceramic body in making in sintering process.Carry out chamfering by the chip behind the table 7 technology sintering, make the corner smooth, interior electrode fully exposes.Carry out the copper termination slurry end-blocking of two end electrodes then.To seal the end product and carry out sintering at nitrogen atmosphere burning end stove, it is as shown in table 8 to burn the end curve, forms the termination electrode of electric capacity, and makes the internal and external electrode combination closely.

Table 7

Parameter	Maximum sintering temperature	Highest temperature temperature retention time	Tempering section oxygen content
				Data	????1280℃	??2.0hr	??50ppm

Table 8

Because external electrode copper is more active metal, very easy generation oxidation in the environment of air or humidity.For making external electrode not oxidized, guarantee the solderability of MLCC product, will handle it, mainly increase by a protective layer on its surface.Be exactly with electric plating method electrode surface plated with nickel and tin outside.To make product and carry out the electrical property detection, its performance is as shown in table 9:

As can be seen from Table 9, good with the properties of product that the method is made, in its capacity set, loss is low, and proof voltage is high and concentrated, and interior electrode and dielectric thickness are even.

Embodiment 2:

Obtain scattered ceramic size with foregoing manufacture craft, become the dielectric film of 10 μ m thickness with film casting machine curtain coating, the crust piece that obtains behind 60 layers of the laminations after lamination and cutting, carries out sintering by table 10 curve.

Table 10

Tested number	Maximum sintering temperature	Highest temperature temperature retention time	Tempering section oxygen content
				????1	????1260℃	????2.0hr	??50ppm
????2	????1280℃	????2.0hr	??50ppm
				????3	????1300℃	????2.0hr	??50ppm
????4	????1320℃	????2.0hr	??50ppm

Chip behind the above-mentioned sintering is carried out chamfering, burns end, plate nickel dam and tin layer in two end electrodes again, it is as shown in table 11 to record electrical property:

Table 11

Tested number	Sintering temperature	Capacity (μ F)	Loss (10 -4)	Insulation (Ω)	Proof voltage (V)	Thickness of electrode (μ m)	Dielectric thickness (μ m)
								??1	??1220℃	??0.96-1.04	??267-301	??＞5*10 9	??480-560	??1.0-1.2	??7.0-7.4
??2	??1240℃	??1.00-1.08	??273-300	??＞5*10 9	??450-580	??1.0-1.2	??6.9-7.3
								??3	??1250℃	??1.03-1.13	??268-290	??＞5*10 9	??460-560	??1.0-1.2	??6.9-7.3
??4	??1270℃	??1.05-1.18	??277-312	??＞5*10 9	??430-540	??1.0-1.2	??6.8-7.2

Table 9

Sample number into spectrum	Firing temperature (℃)	Thickness of electrode (μ m)	Dielectric thickness (μ m)	DIELECTRIC CONSTANT	????tanδ ????(×10 -4)	???????ΔC/C 20℃(％)		?????????????ΔC/C 25℃(％)			25 ℃ of CR long-pending (M Ω uF)	125 ℃ of CR long-pending (M Ω uF)		Average life span (hr)	Number of non-compliances in the high humility load test
																????-25℃	??85℃	??-55	??125	????max	????16V	????16V
						????1*	????1300	??1.0-1.2	??6.9-7.1	Form semiconductor, can not measure
????2	????1300	??1.0-1.2	??6.9-7.2	????3240	????210																	????-3.4	??-6.2	??2.5	??-6.7	????7.2	????6860	????2870	????526		????0
						????3	????1300	??1.0-1.2	??6.9-7.3	????3520	????200	????-4.8	??-7.0	??-3.2	??-6.5	????8.5	????7100	????3500	????603		????0
????4	????1320	??1.0-1.2	??7.1-7.3	????3160	????240																	????-5.2	??-6.3	??-4.3	??-5.8	????7.5	????6840	????2850	????591		????0
						????5*	????1360	??1.0-1.2	??6.9-7.3	Sintering is insufficient, can not measure
????6*	????1300	??1.0-1.2	??7.0-7.3	????3340	????210																	????-4.8	??-5.8	??-6.8	??-6.6	????10.8	????6480	????2960	????195		????0
						????7	????1300	??1.0-1?2	??6.9-7.2	????3340	????220	????-4.4	??-5.2	??-4.5	??-6.9	????7.0	????6840	????2970	????526		????0
????8	????1300	??1.0-1.2	??6.8-7.1	????3520	????220																	????-4.9	??-5.0	??-5.2	??-6.5	????7.5	????6500	????3200	????603		????0
						????9	????1320	??1.0-1.2	??6.9-7.2	????3620	????210	????-4.2	??-5.3	??-3.3	??-5.5	????7.3	????7010	????3000	????581		????0
????10	????1300	??1.0-1.2	??6.7-7.3	????3230	????230																	????-4.8	??-4.3	??-5.3	??-6.5	????8.3	????6710	????2800	????531		????0
						????11*	????1300	??1.0-1.2	??7.1-7.3	????3420	????230	????-3.3	??-6.6	??-3.4	??-6.5	????6.8	????2360	????620	????150		????0
????12*	????1360	??1.0-1.2	??6.9-7.3	Sintering is insufficient, can not measure
																????13	????1280	??1.0-1.2	??7.0-7.3	????3490	????220	????-1.5	??-7.2	??-0.3	??-9.8	????10.5	????5780	????3260	????575		????0
????14	????1300	??1.0-1.2	??6.9-7.2	????3570	????180	????-3.4	??-4.3	??-3.1	??-6.8	????11.5	????5890	????2870	????544		????0
																????15	????1300	??1.0-1.2	??6.8-7.1	????3050	????190	????-2.8	??-5.6	??-2.5	??-6.9	????9.8	????6700	????3200	????603		????0
????16	????1320	??1.0-1.2	??6.9-7.2	????3430	????200	????-1.9	??-6.9	??-1.8	??-8.9	????13.5	????6010	????3300	????530		????0
																????17	????1320	??1.0-1.2	??6.7-7.3	????3330	????150	????-2.6	??-7.8	??-3.0	??-9.1	????10.2	????6210	????3400	????501		????0

Table 9 (continuing)

Sample number into spectrum	Firing temperature (℃)	Thickness of electrode (μ m)	Dielectric thickness (μ m)	DIELECTRIC CONSTANT	????tanδ ????(×10 -4)	??????????ΔC/C 20℃(％)		????????????????ΔC/C 25℃(％)			25 ℃ of CR long-pending (M Ω uF)	125 ℃ of CR long-pending (M Ω uF)	Average life span (hr)	Number of non-compliances in the high humility load test
															????-25℃	????85℃	????-55	????125	????max	????16V	??16V
						????18*	????1320			????3560	????180	????-0.6										????-10.8	????-0.2	????-16.1	????16.1	????5710	??3200	????481	??0
????19*	????1300	??1.0-1.2	????6.9-7.1	????3620	????190								????-3.9	????-15.2	????-3.2	????-16.5	????16.5	????6400	??2700	????453	??0
						????20*	????1320	??1.0-1.2	????6.9-7.2	????3320	????210	????-3.2										????-15.5	????-3.3	????-15.5	????15.5	????7030	??3240	????541	??0
????21*	????1300	??1.0-1.2	????6.9-7.3	????3730	????200								????-4.0	????-14.9	????-4.3	????-16.5	????16.5	????5610	??2970	????438	??0
						????22	????1300	??1.0-1.2	????7.1-7.3	????3680	????170	????-3.6										????-5.3	????-4.1	????-6.9	????11.4	????5450	??2980	????594	??0
????23	????1300	??1.0-1.2	????6.9-7.3	????3250	????210								????-2.7	????-5.6	????-3.5	????-6.7	????9.9	????6540	??3100	????600	??0
						????24	????1320	??1.0-1.2	????7.0-7.3	????3630	????200	????-1.6										????-5.9	????-2.8	????-8.0	????10.5	????5810	??3120	????550	??0
????25*	????1320	??1.0-1.2	????6.9-7.2	????3950	????230								????-4.0	????-16.0	????-4.5	????-18.5	????18.5	????6010	??2980	????450	??0
						????26*	????1360	??1.0-1.2	????6.8-7.1	Sintering is insufficient, can not measure
????27	????1300	??1.0-1.2	????6.9-7.2	????3330	????170																????-3.5	????-5.2	????-4.1	????-6.9	????11.8	????4690	??3180	????594	??0
						????28	????1300	??1.0-1.2	????6.7-7.3	????3240	????210	????-3.7	????-5.0	????-2.5	????-5.7	????9.9	????5780	??3060	????620	??0
????29	????1320	??1.0-1.2	????6.9-7.3	????3530	????220																????-3.5	????-5.0	????-3.8	????-8.3	????9.5	????6790	??3020	????500	??0
						????30	????1300	??1.0-1.2	????7.0-7.3	????3660	????180	????-3.0	????-4.2	????-4.1	????-6.9	????10.4	????5800	??2880	????494	??0
????31	????1320	??1.0-1.2	????6.9-7.2	????3100	????220																????-2.9	????-6.6	????-3.5	????-6.7	????9.9	????6780	??3130	????490	??0
						????32	????1320	??1.0-1.2	????6.8-7.1	????3230	????200	????-2.6	????-4.9	????-2.8	????-8.0	????8.5	????5900	??3420	????500	??0
????33	????1320	??1.0-1.2	????6.9-7.2	????3050	????190																????-2.8	????-5.4	????-3.5	????-6.8	????10.8	????4900	??3000	????493	??0
						????34*	????1300	??1.0-1.2	????6.7-7.3	????3830	????220	????-4.0	????-17.2	????-3.5	????-19.2	????19.2	????5010	??2900	????430	??0

Embodiment 3:

Obtain scattered ceramic size with foregoing manufacture craft, become the dielectric film of 5um, 7um, 10um, 13um thickness, build up the crust piece respectively with same procedure with film casting machine curtain coating.Design specification is as shown in table 13.

By lamination, cutting, binder removal, with carrying out sintering as table 12 technology:

Table 12

Parameter	Maximum sintering temperature	Highest temperature temperature retention time	Tempering section oxygen content
				Data	??1280℃	??2.0hr	??50ppm

Chip behind the above-mentioned sintering is carried out chamfering, burns end, plate nickel dam and tin layer in two end electrodes again, it is as shown in table 13 to record electrical property:

Table 13

Specification	The number of plies	Capacity (nf)	Loss (* 10 -4)	Insulation (Ω)	Proof voltage (V)	Thickness of electrode (um)	Dielectric thickness (um)
								??0402	????20	??10.5-10.9	??235-260	????＞5*10 10	??450-560	??1.1-1.4	??9.4-9.9
????60	??460-495	??284-325	????＞2*10 10	??380-460	??0.9-1.1	??6.5-7.0
							??0603		????60	??95-108	??260-272	????＞1*10 10	??500-590	??1.0-1.2	??8.2-8.6
????100	??215-239	??310-326	????＞5*10 9	??360-370	??0.9-1.1	??6.5-7.0
								????150	??335-349	??350-365	????＞5*10 9	??320-350	??0.8-1.0	??5.4-6.0
??0805	????100	??480-510	??260-285	????＞5*10 9	??420-480	??0.9-1.1									??6.5-7.0
							????150	??1023-1059	??364-376	????＞5*10 9	??300-320	??0.7-0.9	??4.7-5.1
	????250	??3642-3680	??382-406	????＞5*10 9	??250-280	??0.7-0.9								??4.0-4.3

By table 13 data as can be seen, each sample performance of making is good, and in its capacity set, loss value is normal, the proof voltage height, and interior electrode and dielectric thickness are even.

Embodiment 4:

Produce chip behind the sintering with preceding described method, carry out chamfering, end-blocking, burn end with the burning end low-temperature space condition different shown in the table 15 with the high-temperature region oxygen content by table 14:

Table 14

The low-temperature space oxygen content	Sintering follower head situation
		??50ppm	More, the short texture of the inner hole in termination, DF rising, IR descend after the surface treatment
??100ppm	Few, the compact structure of the inner hole in termination, electrical property is normal after the surface treatment
		??200ppm	Few, the compact structure of the inner hole in termination, capacity is on the low side and dispersion, and internal and external electrode connects bad

Table 15

The high-temperature region oxygen content	Sintering follower head situation
		??10	Few, the compact structure of normal, the inner hole of termination color, pulling force is qualified
??15	The termination color is few, the compact structure of red partially, inner hole slightly, and pulling force is qualified
		??20	The termination is black, and oxidation is serious

Claims (10)

1, a kind of chip multilayer ceramic capacitor, comprise interior electrode (1), with dielectric layer (2) interior electrode crossing lamination, that make by the dielectric ceramic material powder and the termination electrode (3) that is connected with the interior electrode (1) of deriving, the number of plies of described dielectric layer (2) is the 20-500 layer, thickness is 2-20 μ m after the burning of every layer of dielectric layer, in every layer after the burning of electrode (1) thickness be 0.5-2.0 μ m;

It is characterized in that described dielectric ceramic material powder comprises key component and accessory constituent, wherein:

The chemical constitution formula of described key component is Ba _1-x-ySr _xCa _yTiO ₃, in the formula, 0.05≤x≤0.4,0.01≤y≤0.25;

Described accessory constituent comprises first accessory constituent and second accessory constituent again, and wherein said first accessory constituent is: α Y ₂O ₃+ β MgO+ (1-alpha-beta) MnO, in the formula, α, β represent mol ratio, its scope is 0.2≤α≤0.8,0.1≤β≤0.6; Described second accessory constituent is SiO ₂-TiO ₂-Al ₂O ₃

And with respect to described key component, the weight percentage of described first accessory constituent is 0.2wt.%～2.0wt.%; The weight percentage of described second accessory constituent is 0.2wt.%～5.0wt.%.

2, ceramic capacitor as claimed in claim 1 is characterized in that, wants component S iO the described second time ₂-TiO ₂-Al ₂O ₃In the mol ratio of each oxide be:

SiO ₂∶TiO ₂∶Al ₂O ₃＝0.2-1.8∶0.2-1.8∶0.2-1.8。

3, ceramic capacitor as claimed in claim 1 is characterized in that, described interior electrode is to be made by nickel or nickel alloy.

4, ceramic capacitor as claimed in claim 1 is characterized in that, described termination electrode is to be made by copper or copper alloy.

5, ceramic capacitor as claimed in claim 1 is characterized in that, the nickel slurry printing that the interior electrode employing nickel powder granularity of being gone back is 0.1-0.4 μ m is made, and the nickel of electrode heavily is 5.0-7.0 milligram/square inch in the gained.

6, ceramic capacitor as claimed in claim 5 is characterized in that, also is added with BaTiO in the described nickel powder ₃Ceramic powder, its ratio is between 100/13-100/25.

7, a kind of preparation is as the method for one of claim 1-6 described chip multilayer ceramic capacitor, comprise: mix slurry, make the medium diaphragm, replace electrode and dielectric layer, lamination, cutting, binder removal, sintering, end-blocking electrode in the double exposure, burn end, nickel plating and zinc-plated operation, it is characterized in that above-mentioned binder removal operation is at N ₂Carry out under the protection of atmosphere; Above-mentioned sintering circuit is divided into heat up section, the high temperature section of burning till and temper section, and wherein, heat up section and the high temperature section of burning till are to contain H ₂N ₂Carry out H under the atmosphere protection ₂Content is controlled at the 0.05-5% of atmosphere total amount, and the sintering temperature of the high temperature section of burning till is controlled at 1200 ℃-1400 ℃, and the temper section is the N in oxidizability ₂Carry out in the atmosphere, wherein, O ₂Content is 10ppm-100ppm, and the temperature of temper section is 800 ℃-1050 ℃.

8, method as claimed in claim 7 is characterized in that, O in the described temper ₂Content be 30ppm-80ppm.

9, method as claimed in claim 7 is characterized in that, described burning end operation is to contain O ₂N ₂Segmentation is carried out in the atmosphere, wherein, is the low-temperature zone of described burning end operation below 500 ℃, and 500 ℃ is the high temperature section of described burning end operation to burning the end maximum temperature, and burning the end maximum temperature is 700 ℃-1050 ℃, and N in the described low-temperature zone ₂Oxygen content in the atmosphere will be higher than the N of described high temperature section ₂Oxygen content in the atmosphere, described low-temperature zone N ₂Oxygen content in the atmosphere is 50-400ppm, described high temperature section N ₂Oxygen content in the atmosphere is 0-50ppm.

10, method as claimed in claim 9 is characterized in that, described burning end maximum temperature is 800 ℃-950 ℃, N in the described low-temperature zone ₂Oxygen content in the atmosphere is 100-300ppm, N in the described high temperature section ₂Oxygen content in the atmosphere is 0-30ppm.