CN1581387A - Multi-layer ceramic capacitor, and its preparing method and dielectric ceramic material used therefor - Google Patents
Multi-layer ceramic capacitor, and its preparing method and dielectric ceramic material used therefor Download PDFInfo
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Abstract
Y5V 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, Ca, Zr, and general expression is (Ba1-X-YCaXSry)2 (Ti 1-Z Zrz)O3,the dielectric layer also includes one or more following materials: 0.1-5wt% Mn2O3, MnCO3, MnO2, Nb2O5, NiO etc. The invention prepares laminar ceramic capacitor in large capacity and number of layers, and lowered production cost.
Description
Technical field
The present invention relates to a kind of ceramic capacitor and manufacture method thereof and used dielectric ceramic material powder, more particularly, the present invention relates to a kind of Y5V type multiple-layer sheet ceramic capacitor and preparation method thereof and used dielectric ceramic material powder.
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 Y5V 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 Y5V 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 Y5V type multilayer sheet type ceramic capacitor (MLCC) extensively adopts precious metals ag/Pd material, and for the high product of some quality requirements even adopt electrode in the full Pd, termination electrode then is Ag or AgO.Low fever's system in the general employing of the MLCC product of Ag/Pd system, sintering in air atmosphere.The technical development time of this system is longer, the technology comparative maturity of each operation, thereby have the advantage of following main aspect:
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 employed ceramic dielectric system does not need to have resistance to reduction, so raw-material making is simple relatively, the manufacturing cost of device therefor is also relatively low;
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;
And the ceramic body sintering of this middle low fever's system can carry out at a lower temperature, also is beneficial to the cost that cuts down the consumption of energy.
But there are many deficiencies in the MLCC product of Ag/Pd system:
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 low fever's system in the employing of Ag/Pd system Y5V 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 Y5V 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 Y5V 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 chemical composition general formula that is used for preparing the dielectric ceramic material powder of dielectric layer among the present invention is:
(Ba
1-xCa
xSr
y)
m(Ti
1-zZr
z)O
3+A，
In the formula,
A is for being selected from Mn
2O
3, MnCO
3, MnO
2, Nb
2O
5, NiO, Y
2O
3, ZnO, Yb
2O
3, Er
2O
3, Ho
2O
3And SiO
2In a kind of material or the mixture of several materials, its weight percentage in described dielectric ceramic material powder is 0.1wt.%～2wt.%;
x＝0.005～0.14；
y＝0.04～0.19
z＝0.16～0.24；
m＝1.001～1.03。
Among the present invention, the Ca in the dielectric ceramic material powder
2+Can be with CaO or CaCO
3Form add; Mn in the dielectric ceramic material powder
2+Can be with Mn
2O
3, MnO
2Or MnCO
3Form add, its weight percentage that accounts for dielectric ceramic material is 0.05wt.%～0.5wt.%; Preferably, be Mn
2O
3, Y
2O
3, SiO
2In one or more, its weight percentage in described dielectric ceramic material powder is 0.3wt.%～1.6wt.%.
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 inorganic additive such as 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 dielectric ceramic material powder for preparing multilayer ceramic capacitor, the chemical composition general formula of this dielectric ceramic material powder is:
(Ba
1-xCa
xSr
y)
m(Ti
1-zZr
z)O
3+A，
In the formula,
A is for being selected from Mn
2O
3, MnCO
3, MnO
2, Nb
2O
5, NiO, Y
2O
3, ZnO, Yb
2O
3, Er
2O
3, Ho
2O
3And SiO
2In a kind of material or the mixture of several materials, its weight percentage in described dielectric ceramic material powder is 0.1wt.%～2wt.%;
x＝0.005～0.14；
y＝0.04～0.19
z＝0.16～0.24；
m＝1.001～1.03。
Preferably, A is Mn
2O
3, Y
2O
3, SiO
2In one or more, its weight percentage in described dielectric ceramic material powder is 0.3wt.%～1.6wt.%.
Again on the one 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 5-500ppm, and the temperature of temper section is 800 ℃-1050 ℃.
Preferably, O in the temper section
2Content be 25-45ppm.
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.
In the present invention, ceramic dielectric body has adopted the dielectric ceramic composition with resistance to reduction Y5V characteristic.The main component of this ceramic powder is the composite oxides of Ba, Ti, Ca, Zr, and its general formula is (Ba
1-X-YCa
XSr
Y)
a(Ti
1-ZZr
Z) O
3, and the mol ratio of two valencys and tetravalent oxide is adjusted between the 1.002-1.030.And this dielectric material also comprise 0.1-5wt%, MnCO
3, MnO
2, Nb
2O
5, NiO, Y
2O
3, ZnO, Yb
2O
3, Er
2O
3, Ho
2O
3And SiO
2In one or more.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 to make, and as adopting Ni or Ni alloy, 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 Y5V 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
A, dielectric ceramic material powder
Preparing multilayer ceramic capacitor of the present invention can adopt conventional porcelain production technology to prepare; The main raw material(s) that is adopted comprises hydro thermal method BaTiO
3, solid phase synthesis BaZrO
3Deng.Ca
2+Then with CaO or CaCO
3Form add Mn
2+With Mn
2O
3, MnO
2Or MnCO
3Form add, other then adds with oxide form.
BaTiO
3Crystal has ABO
3The type perovskite structure.With molar ratio computing, at the BaTiO of A/B greater than 1 (1.00-1.03)
3Mix foreign ion in the composition, and manage to make foreign ion to enter the B position and rise and be subjected to main effect, the oxygen vacancy concentration that causes when alms giver effect is during greater than the oxygen vacancy concentration of oxygen volatilization, and the electron concentration on the Ti position is inhibited, thereby makes porcelain sintering under reducing atmosphere have higher insulation resistivity.Because of Ca
2+Might replace Ba
2+The position, so the resistance to reduction energy and the BaTiO of porcelain
3Middle Ca
2+Concentration is relevant, and is along with Ca
2+The increase of concentration, it is poor more that resistance to reduction becomes, and this just need add more Ca
2+((Ba+Ca)/Ti) could guarantee that porcelain has the good insulation performance performance under reducing atmosphere to increase A/B.
As seen adding percentage by weight by table (1) is 0.2%～4.52
%CaO (or CaCO
3), can make A/B greater than 1.While addition and BaTiO
3Middle Ca
2+Concentration is relevant, Ca
2+Concentration is high more, need add Ca the more, finally causes A/B to increase, and this may be because Ca
2+Existence cause adding the easier A of entering of Ca position, the A position since entering of Ca make Ba
2+Residue, and it is generally acknowledged Ba
2+Can not enter the B position, only Ca under the situation that adds abundant Ca
2+Just enter the B position and play a part to suppress electron concentration, porcelain just has resistance to reduction.
Work as BaTiO
3In contain low Ca
2+During concentration, the adding percentage by weight is 0.05～0.5 MnCO in the porcelain prescription
3, porcelain can obtain good insulation resistivity equally.MnCO
3Content to the influence of resistivity shown in figure (2).MnCO
3Adding very little to the resistivity effects that adds the Ca sample, but improved the compactness of porcelain body.This illustrates MnCO
3The following Mn of the lower situation of A/B that is added in (≈ 1)
2+Can enter the A position, improve A/B compared with improve the porcelain resistance to reduction can effect, on the other hand, make A/B＞1 or add enough MnCO adding Ca
3Situation under, Mn
2+Enter crystal boundary again, thereby improve the sintering character of porcelain body.MnO
2Interpolation have identical effect.
The present invention adds Nb
5+, Nb
5+Be donor doping, so Nb
5+Be added with the raising that is beneficial to DIELECTRIC CONSTANT.In molar content, work as Ca
2+Content greater than Nb
5+During the twice of content, Ti
4+Locational Ca
2+Ion has compensated donor ion Nb as acceptor ion
5+, and prevented Ti
4+Be reduced to Ti
3+
The adding percentage by weight is 0.02%～1.0% NiO, 0.1%～3.0%SiO
2Or Y
2O
3, ZnO, Yb
2O
3, Er
2O
3, Ho
2O
3In a kind of or with several, help making porcelain body in the burning temperature scope of broad, to keep thin brilliant.
The preparation process of B, chip multilayer ceramic capacitor:
(1) dielectric material is mixed with PVB (polyvinyl butyral resin), add 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 carries out lamination and cuts into raw cook;
(5) raw cook is carried out binder removal after, adopt segmented gas-protecting sintering technology, reducing atmosphere (
With N
2And H
2Mixing by a certain percentage) carries out sintering in 1200 ℃-1400 ℃ in; Then, at oxidizing atmosphere (with N
2And H
2Mix by a certain percentage) in carry out temper in 850 ℃-1050 ℃, obtain the chip behind the sintering;
(6) chip behind the above-mentioned sintering is carried out chamfering, end-blocking;
(7) with the chip behind the end-blocking at N
2Burn end in 700 ℃ of-1050 ℃ of temperature under the protective atmosphere;
(8) will burn end back gained chip and carry out the nickel plating of two end electrodes and zinc-plated, make described Y5V matrix formula multilayer ceramic capacitor.
In said method, the sintering circuit in the step (4) is one of most important technology during whole Y5V matrix formula multilayer ceramic capacitor is made.Because electrode is metal Ni 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 porcelain powder, 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 1-5%.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 20,30 respectively, the result of the oxygen content of 50ppm.
Table 1
| Tested number | Tempering section oxygen content | High fever temperature | ????DF(×10 -4) | ??25℃，IR(Ω) |
| ??1 | ??20ppm/900℃/3Hr | ??1220℃/2Hr | ????269～325 | ??5×10 9 |
| ??2 | ??30ppm/900℃/3Hr | ??1220℃/2Hr | ????256～311 | ??5×10 9 |
| ??3 | ??50ppm/900℃/3Hr | ??1220℃/2Hr | ????315～420 | ??5×10 9 |
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 20ppm, 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 50ppm 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 30ppm 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, very crucial 950 ℃ of controls to the heating rate of highest temperature section, major parameter is 1-5 ℃/min.
N in the step (7)
2Burning end operation 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 of step (7), at this temperature section, organic resin decomposes; 500 ℃-burning end maximum temperature is the high-temperature region of step (7), burns the end maximum temperature and generally is controlled at 700 ℃-1050 ℃, is preferably 800 ℃-1000 ℃.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.
In addition, make Y5V matrix formula multilayer ceramic capacitor run into the most difficult problem be insulation resistance (IR) repeatedly.Insulation resistance is placed the phenomenon that a period of time appearance insulation descends after being meant the product electric performance test repeatedly.
Insulation resistance main cause repeatedly is that the contraction of porcelain film and nickel slurry is inconsistent, and micro-crack appears in inside, causes product to occur descending placing a period of time IR.For this reason, we mainly adjust on the nickel slurry.By the selection to 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 with medium better, and nothing is than slit generation greatly.It is heavy to reduce nickel, and it is too big to avoid the nickel slurry to shrink, and reduces internal stress, overcomes IR problem repeatedly.
Table 2
| Tested number | Nickel powder granularity (D50) | IR is ratio repeatedly |
| ????1 | ????0.30um | ????0.03‰ |
| ????2 | ????0.50um | ????0.1‰ |
| ????3 | ????0.80um | ????1.0‰ |
Table 3
| Tested number | Nickel powder/inorganic additive | IR is ratio repeatedly |
| ????1 | ????100/10 | ????0.2‰ |
| ????2 | ????100/20 | ????0.01‰ |
| ????3 | ????100/30 | ????0.3‰ |
Table 4
| Tested number | Nickel is heavy | IR is ratio repeatedly |
| ????1 | 5.0 milligram/square inch | Do not have |
| ????2 | 8.5 milligram/square inch | ????0.05‰ |
| ????3 | 11.0 milligram/square inch | ????0.1‰ |
Analyze as can be seen by the data in his-and-hers watches 2, the table 3, the making nickel powder granularity of interior electrode nickel slurry is controlled at 0.1-0.4um, and nickel powder/inorganic additive proportional control is between 100/13-100/25.Interior electrode nickel slurry printing nickel heavily is controlled at 5.0-7.0 milligram/square inch.
Embodiment 1:
Get 4000g nickel electrode Y5V type dielectric material, its prescription is as shown in table 5 below:
Table 5
| Sample | ?????????(Ba 1-x-yCa xSr y) m(Ti 1-zZr z)O 3 | The percentage by weight of each helper component (wt%) | |||||
| ??x | ??y | ??z | ??m | ????Y 2O 3 | ????Mn 2O 3 | ????SiO 2 | |
| ??1 | ??0.05 | ??0.125 | ??0.175 | ??1.0013 | ????0.24 | ????0.17 | ????0.24 |
| ??2 | ??0.02 | ??0.155 | ??0.189 | ??1.0023 | ????0.14 | ????0.10 | ????0.14 |
| ??3 | ??0.08 | ??0.090 | ??0.210 | ??1.0033 | ????0.24 | ????0.37 | ????0.44 |
| ??4 | ??0.10 | ??0.070 | ??0.160 | ??1.0030 | ????0.22 | ????0.21 | ????0.14 |
| ??5 | ??0.12 | ??0.050 | ??0.230 | ??1.0023 | ????0.24 | ????0.24 | ????0.83 |
| ??6 | ??0.01 | ??0.180 | ??0.175 | ??1.0023 | ????0.28 | ????0.17 | ????0.24 |
| ??7 | ??0.05 | ??0.160 | ??0.175 | ??1.0023 | ????0.31 | ????0.17 | ????0.24 |
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 to Roll 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 6 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 6
| Parameter | Maximum sintering temperature | Highest temperature temperature retention time | Tempering section oxygen content |
| Data | ??1220℃ | ??2.5hr | ??30ppm |
Table 7
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 8:
Table 8
| Sample | Sintering temperature (℃) | Capacity (uF) | Loss (10 -4) | Insulation (Ω) | Proof voltage (V) | Thickness of electrode (um) | Dielectric thickness (um) | Dielectric constant |
| ??1 | ??1220℃ | ??1.01-1.14 | ??389-432 | ??＞10 9 | ??400-580 | ??1.0-1.2 | ??6.9-7.1 | ??11678 |
| ??2 | ??1220℃ | ??1.06-1.14 | ??402-462 | ??＞10 9 | ??420-580 | ??1.0-1.2 | ??6.9-7.2 | ??12054 |
| ??3 | ??1220℃ | ??1.09-1.18 | ??469-497 | ??＞10 9 | ??410-550 | ??1.0-1.2 | ??6.9-7.3 | ??12696 |
| ??4 | ??1220℃ | ??0.96-1.04 | ??329-397 | ??＞10 9 | ??400-550 | ??1.0-1.2 | ??7.1-7.3 | ??10893 |
| ??5 | ??1220℃ | ??0.86-0.98 | ??302-347 | ??＞10 9 | ??420-550 | ??1.0-1.2 | ??6.9-7.3 | ??9890 |
| ??6 | ??1220℃ | ??0.90-0.99 | ??345-377 | ??＞10 9 | ??440-580 | ??1.0-1.2 | ??7.0-7.3 | ??9392 |
| ??7 | ??1220℃ | ??0.76-0.84 | ??269-307 | ??＞10 9 | ??420-560 | ??1.0-1.2 | ??6.9-7.2 | ??8896 |
As can be seen from Table 8, 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 10um 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 9 curve.
Table 9
| Tested number | Maximum sintering temperature | Highest temperature temperature retention time | Tempering section oxygen content |
| ????1 | ????1200℃ | ????2.5hr | ??30ppm |
| ????2 | ????1220℃ | ????2.5hr | ??30ppm |
| ????3 | ????1240℃ | ????2.5hr | ??30ppm |
| ????4 | ????1250℃ | ????2.5hr | ??30ppm |
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 10 to record electrical property:
Table 11
| Tested number | Sintering temperature | Capacity (uF) | Loss (10 -4) | Insulation (Ω) | Proof voltage (V) | Thickness of electrode (um) | Dielectric thickness (um) |
| ??1 | ??1200℃ | ??0.96-1.04 | ??360-401 | ??＞10 9 | ??480-560 | ??1.0-1.2 | ??7.0-7.4 |
| ??2 | ??1220℃ | ??1.00-1.08 | ??389-432 | ??＞10 9 | ??450-580 | ??1.0-1.2 | ??6.9-7.3 |
| ??3 | ??1240℃ | ??1.03-1.13 | ??397-465 | ??＞10 9 | ??460-560 | ??1.0-1.2 | ??6.9-7.3 |
| ??4 | ??1250℃ | ??1.05-1.18 | ??399-489 | ??＞10 9 | ??430-540 | ??1.0-1.2 | ??6.8-7.2 |
Embodiment 3:
Obtain scattered ceramic size with foregoing manufacture craft, become the dielectric film of 5um, 7um, 10um, 13um thickness with film casting machine curtain coating, build up the crust piece respectively with same procedure, design specification is as shown in table 8.
By lamination, cutting, binder removal, with carrying out sintering as table 11 technology:
Table 11
| Parameter | Maximum sintering temperature | Highest temperature temperature retention time | Tempering section oxygen content |
| Data | ??1220℃ | ??2.5hr | ??30ppm |
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 12 to record electrical property:
Table 12
| Specification | The number of plies | Capacity (uF) | Loss (* 10 -4) | Insulation (Ω) | Proof voltage (V) | Thickness of electrode (um) | Dielectric thickness (um) |
| ??0402 | ????20 | ??0.032-0.035 | ??250-290 | ??＞2*10 10 | ??760-810 | ??1.1-1.4 | ??9.4-9.9 |
| ????60 | ??0.15-0.17 | ??480-570 | ??＞4*10 9 | ??390-480 | ??0.9-1.1 | ??6.5-7.0 | |
| ??0603 | ????60 | ??0.33-0.35 | ??380-470 | ??＞2*10 9 | ??490-580 | ??1.0-1.2 | ??8.2-8.6 |
| ????100 | ??1.01-1.12 | ??562-689 | ??＞6*10 8 | ??360-450 | ??0.9-1.1 | ??6.5-7.0 | |
| ????150 | ??2.24-2.33 | ??646-785 | ??＞4*10 8 | ??300-450 | ??0.8-1.0 | ??5.4-6.0 | |
| ??0805 | ????100 | ??1.56-1.67 | ??469-514 | ??＞5*10 8 | ??360-450 | ??0.9-1.1 | ??6.5-7.0 |
| ????150 | ??4.87-4.98 | ??656-775 | ??＞2*10 8 | ??280-350 | ??0.7-0.9 | ??4.7-5.1 | |
| ????250 | ??10.3-10.9 | ??857-896 | ??＞6*10 7 | ??250-300 | ??0.7-0.9 | ??4.0-4.3 |
By table 12 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:
Chip with producing with preceding described method behind the sintering carries out chamfering, end-blocking, burns end by table 13 with the burning end low-temperature space condition different with the high-temperature region oxygen content shown in the table 14:
Table 13
| 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 14
| The high-temperature region oxygen content | Sintering follower head situation |
| ??5 | Few, the compact structure of normal, the inner hole of termination color, pulling force is qualified |
| ??10 | The termination color is few, the compact structure of red partially, inner hole slightly, and pulling force is qualified |
| ??15 | The termination is black, and oxidation is serious |
Claims (10)
1, a kind of chip multilayer ceramic capacitor, comprise 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 described 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;
It is characterized in that the chemical composition general formula that constitutes the dielectric ceramic material powder of described dielectric layer is:
(Ba
1-xCa
xSr
y)
m(Ti
1-zZr
z)O
3+A，
In the formula,
A is for being selected from Mn
2O
3, MnCO
3, MnO
2, Nb
2O
5, NiO, Y
2O
3, ZnO, Yb
2O
3, Er
2O
3, Ho
2O
3And SiO
2In a kind of material or the mixture of several materials, its weight percentage in described dielectric ceramic material powder is 0.1wt.%～2wt.%;
x＝0.005～0.14；
y＝0.04～0.19
z＝0.16～0.24；
m＝1.001～1.03。
2, ceramic capacitor as claimed in claim 1 is characterized in that, constitutes the Ca in the dielectric ceramic material powder of described dielectric layer
2+Be with CaO or CaCO
3Form add.
3, ceramic capacitor as claimed in claim 1 is characterized in that, constitutes the Mn in the dielectric ceramic material powder of described dielectric layer
2+Be with Mn
2O
3, MnO
2Or MnCO
3Form add, its weight percentage in described dielectric ceramic material powder is 0.05wt.%～0.5wt.%.
4, ceramic capacitor as claimed in claim 1 is characterized in that, the A that constitutes in the dielectric ceramic material powder of described dielectric layer is Mn
2O
3, Y
2O
3, SiO
2In one or more, its weight percentage in described dielectric ceramic material powder is 0.3wt.%～1.6wt.%.
5, ceramic capacitor as claimed in claim 1 is characterized in that, described interior electrode is to be made by nickel or nickel alloy; Described termination electrode is to be made by copper or copper alloy.
6, ceramic capacitor as claimed in claim 1 is characterized in that, described in electrode be that to adopt the nickel powder granularity be that the nickel slurry printing of 0.1-0.4 μ m is made, the nickel of electrode heavily is 5.0-7.0 milligram/square inch in the gained.
7, a kind of dielectric ceramic material powder that is used to prepare multilayer ceramic capacitor is characterized in that, the chemical composition general formula of described dielectric ceramic material powder is:
(Ba
1-xCa
xSr
y)
m(Ti
1-zZr
z)O
3+A，
In the formula,
A is for being selected from Mn
2O
3, MnCO
3, MnO
2, Nb
2O
5, NiO, Y
2O
3, ZnO, Yb
2O
3, Er
2O
3, Ho
2O
3And SiO
2In a kind of material or the mixture of several materials, its weight percentage in described dielectric ceramic material powder is 0.1wt.%～2wt.%;
x＝0.005～0.14；
y＝0.04～0.19
z＝0.16～0.24；
m＝1.001～1.03。
8, the dielectric ceramic material powder of described dielectric layer as claimed in claim 7 is characterized in that, the A in the described dielectric ceramic material powder is Mn
2O
3, Y
2O
3, SiO
2In one or more, its weight percentage in described dielectric ceramic material powder is 0.3wt.%～1.6wt.%.
9, 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, is preferably 1-5%; The sintering temperature of the high temperature section of burning till is controlled at 1200 ℃-1400 ℃; The temper section is the N in oxidizability
2Carry out in the atmosphere, wherein, O
2Content is 5-50ppm, is preferably 25-45ppm, and the temperature of temper section is 800 ℃-1050 ℃.
10, method as claimed in claim 9 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, is preferably 100-300ppm; Described high temperature section N
2Oxygen content in the atmosphere is 0-50ppm, is preferably 0-30ppm.
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|---|---|---|---|
| CNB031401104A CN100403467C (en) | 2003-08-08 | 2003-08-08 | Multi-layer ceramic capacitor, and its preparing method and dielectric ceramic material used therefor |
Publications (2)
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|---|---|
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| CN100403467C CN100403467C (en) | 2008-07-16 |
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