CN100524554C - Method of production of multilayer ceramic electronic device - Google Patents
Method of production of multilayer ceramic electronic device Download PDFInfo
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- CN100524554C CN100524554C CNB2004101005386A CN200410100538A CN100524554C CN 100524554 C CN100524554 C CN 100524554C CN B2004101005386 A CNB2004101005386 A CN B2004101005386A CN 200410100538 A CN200410100538 A CN 200410100538A CN 100524554 C CN100524554 C CN 100524554C
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Abstract
A method of production of a multilayer ceramic capacitor or other multilayer ceramic electronic device with few structural defects and improved highly accelerated life, that is, a method of production of a multilayer ceramic electronic device having a firing step of firing a stack comprised of a dielectric layer paste and an internal electrode layer paste including a base metal alternately arranged in a plurality of layers, a first annealing step of annealing, at a temperature T 1 of 600 to 900 DEG C., the stack after firing and a second annealing step of annealing, at a temperature T 2 of 900 to 1200 DEG C. (however, excluding 900 DEG C.), the stack after said first annealing.
Description
Technical field
The present invention relates to the manufacture method of multilayer ceramic electronic components such as multilayer ceramic capacitor.
Background technology
In recent years, constitute constituent material, can use cheap base metal such as nickel to replace expensive noble metal such as platinum or palladium, reduced cost significantly as the interior electrode layer of the multilayer ceramic capacitor of multilayer ceramic electronic component one example.
But, for the metallization of the interior electrode layer that suitably uses base metal, need be at sintering raw cook under the reducing atmosphere.Also have, the sintering under the reducing atmosphere is had reducing resistance, need in the contained dielectric substance layer of raw cook, add Mn in order to make dielectric material.Further, under reducing atmosphere, behind the sintering,, need apply annealing in process to this sintered body in order to reoxidize the dielectric substance layer in the sintered body.
In the past, when in this dielectric substance layer, adding Mn, if not to sintering the sintered body that contains behind the raw cook of this dielectric substance layer carry out suitable annealing in process, MnO near the interior electrode layer or end, causes the problem such as interrupted of fault of construction or interior electrode layer with segregation (separating out).That is,, then become the reason that the rate of finished products of capacitor and reliability etc. descend if annealing in process can not suitably be carried out.
Method in the past is, behind the sintering raw cook, the gained sintered body keep as the condition of 1000～1200 ℃ of left and right sides temperature under only carry out annealing in process (with reference to patent documentation 1: the spy opens 2002-80279 communique and patent documentation 2: the spy opens flat 8-8137 communique).
But, when only carrying out an annealing in process,, then have the tendencies such as abundant inadequately, that insulation resistance worsens, its accelerated aging (high-temperature load life-span) also shortens that reoxidize of dielectric substance layer if keep temperature low excessively.On the contrary, if keep temperature too high, though then reoxidizing of dielectric substance layer carried out smoothly, but be oxidizing to interior electrode layer, therefore not only capacity reduces, and reacts the tendency that exists capacity temperature characteristic, insulation resistance and accelerated aging thereof to worsen with the dielectric medium matrix.
That is,, then be difficult to make its stable (maintenance) temperature or time to be able to optimization if only carry out annealing in process one time.
Summary of the invention
The object of the present invention is to provide fault of construction few and improved the manufacture method of the multilayer ceramic electronic components such as multilayer ceramic capacitor in high-temperature load life-span.
Present inventors find, repeatedly carry out annealing in process behind the sintering by stage, can reach goal of the invention, so that finish the present invention.
Promptly, manufacture method according to the invention provides a kind of multilayer ceramic electronic component is characterized in that: have a plurality of dielectric substance layers of the mutual configuration of sintering with paste with contain the base metal interior electrode layer carries out annealing in process to the 1st for 2 times in the temperature T that is higher than temperature T 1 with the sintering circuit of the laminate of paste, the laminate of the laminate behind this sintering after temperature T is carried out the 1st annealing operation of annealing in process for 1 time and annealed the 2nd annealing operation.
According to the present invention, a kind of manufacture method of multilayer ceramic electronic component is provided, it is characterized in that: have a plurality of dielectric substance layers of the mutual configuration of sintering with paste with contain the base metal interior electrode layer carries out annealing in process to the 1st for 2 times in the temperature T of 900～1200 ℃ (not containing 900 ℃) with the sintering circuit of the laminate of paste, the laminate of the laminate behind this sintering after 600～900 ℃ temperature T is carried out the 1st annealing operation of annealing in process for 1 time and annealed the 2nd annealing operation.
Preferred described T2 and described T1 poor (T2-T1) is more than 50 ℃.
Among the present invention, the 1st annealing operation and the 2nd annealing operation can be followed sintering circuit and carry out continuously, also can be independent of sintering circuit and carry out.
Carry out continuously one for example down.
For example, the described atmosphere temperature of cooling process that keeps temperature to reduce the described sintering circuit of atmosphere temperature from sintering is reduced to the temperature identical with described temperature T 1, carries out described the 1st annealing operation, carry out described the 2nd annealing operation then.
Also have, the atmosphere temperature of the cooling process of sintering circuit be reduced to be lower than described temperature T 1 and be higher than the temperature of room temperature after, improve atmosphere temperature, carry out described the 1st annealing operation, carry out described the 2nd annealing operation then.
Independently carry out one for example down.
For example, after the cooling process of sintering circuit finishes, improve atmosphere temperature, carry out described the 1st annealing operation, carry out described the 2nd annealing operation then.
Preferred described the 1st annealing operation is 10
-7Carry out in the partial pressure of oxygen of～0.1Pa, described the 2nd annealing operation is 10
-5Carry out under the partial pressure of oxygen of～10Pa.
The preferred dielectric substance layer that uses has with paste: contain and consist of [(Sr
1-xCa
x) O]
m(Ti
1-yZr
y) O
2, wherein x is that 0 ≦ x ≦ 1.00, y are that 0 ≦ y ≦ 1.00, m are the principal component raw material and the accessory ingredient raw material that contains Mn of the dielectric medium oxide of 0.75 ≦ m ≦ 1.3.
The preferred dielectric substance layer that uses has with paste: contain and consist of [(Sr
1-xCa
x) O]
m(Ti
1-yZr
y) O
2, wherein x be 0 ≦ x ≦ 1.00, y be 0 ≦ y ≦ 0.20, m be 0.94 ≦ m ≦ 1.02 the dielectric medium oxide the principal component raw material and
Containing the content that is selected from respect to 100 moles of these principal component raw materials is the Mn oxide that is scaled 4 moles of less thaies with Mn in the oxide, with respect to the content of 100 moles of principal component raw materials for be scaled with rare earth element 0.02～2 mole (not containing 2 moles) by Sc, the oxide of the rare earth element that Y and lanthanide series constitute, content with respect to 100 moles of principal component raw materials is the V that is selected from of 0.01～2 mole (not containing 2 moles), Nb, W, more than one materials in the oxide of Ta and Mo, the content that reaches with respect to 100 moles of principal component raw materials is the SiO that is selected from of 0～15 mole (not containing 0 mole and 15 moles)
2, MO (wherein M is at least a element that is selected among Ba, Ca, Sr and the Mg), Li
2O and B
2O
3In the accessory ingredient raw material of more than one materials.
The preferred dielectric substance layer that uses has with paste: contain and consist of [(Ca
xSr
1-x) O]
m[(Ti
yZr
1-y) O
2], wherein x, y, m are the principal component raw material of the dielectric medium oxide of 0 ≦ x ≦ 1,0 ≦ y ≦ 0.10,0.75 ≦ m ≦ 1.04,
With contain content with respect to 100 moles of these principal component raw materials be that to be converted into MnO be 0.2～5 mole Mn oxide, with respect to the content of 100 moles of principal component raw materials for being converted into Al
2O
3Be 0.1～10 mole of Al oxide, contain and consist of [(Ba
zCa
1-z) O]
vSiO
2, wherein z and v be the composite oxides of 0 ≦ z ≦ 1,0.5 ≦ v ≦ 4.0, be 0.5～15 mole composite oxides, and be that more than one of 0.02～1.5 mole are selected from the accessory ingredient raw material of the oxide of rare earth element, Nb, Mo, Ta and W with respect to the content of 100 moles of principal component raw materials with respect to the content of 100 moles of principal component raw materials.
The preferred dielectric substance layer that uses has to contain with paste and consists of [(Ca
1-xMe
x) O] m (Zr
1-yTi
y) O
2, wherein Me is more than one elements that are selected from Sr, Mg and Ba, and x is that 0 ≦ x ≦ 1.00, y are that 0.1 ≦ y ≦ 0.8, m are the principal component raw material of the dielectric medium oxide of 0.8 ≦ m ≦ 1.3,
With contain content with respect to 100 moles of these principal component raw materials for being converted into V
2O
5Be the V oxide of 0～7 mole (not containing 0 mole and 7 moles), with respect to the content of 100 moles of principal component raw materials for being converted into Al
2O
3Be 0～15 mole of (not containing 0 mole and 15 moles) Al oxide, with respect to the content of 100 moles of principal component raw materials be that to be converted into Mn in the oxide be 0～5 mole of (not containing 0 mole and 5 moles) Mn oxide, with respect to the content of 100 moles of principal component raw materials for be scaled the SiO that is selected from of 0～20 mole (not containing 0 mole and 20 moles) with oxide
2, MO (wherein M is at least a element that is selected among Ba, Ca, Sr and the Mg), Li
2O and B
2O
3More than one materials and the accessory ingredient raw material of the oxide of rare earth element.
According to the present invention, carrying out interim repeatedly annealing in process as the optimization means of annealing conditions.Thus, can suppress in the past near interior electrode layer and the segregation of the MnO that the end takes place, separate out faults of construction such as the circuit turn-on that causes is bad.Its result has eliminated the interrupted phenomenon of the interior electrode layer that fault of construction causes, helps to improve the coverage rate of interior electrode layer, raising capacity (or preventing to descend).
Also have, can improve the insulation resistance and the accelerated aging (high-temperature load life-span) thereof of multilayer ceramic electronic component such as gained multilayer ceramic capacitor.
Do not do special qualification for multilayer ceramic electronic component, but can enumerate mounted on surface (SMD) sheet type electronic units such as multilayer ceramic capacitor, piezoelectricity lamination body component, sheet voltage-sensitive resistor, flake thermistor.
Description of drawings
Below based on the explanation of embodiment shown in accompanying drawing the present invention, here:
Fig. 1 is the profile of the multilayer ceramic capacitor of one embodiment of the invention.
Fig. 2～4 are the figure of each variations in temperature of sintering, the 1st annealing and the 2nd annealing of explanation one embodiment of the invention.
Embodiment
As shown in Figure 1, has the capacitor element main body 10 that a plurality of dielectric substance layers 2 of mutual configuration and interior electrode layer 3 form by the multilayer ceramic capacitor 1 as an example of multilayer ceramic electronic component of the inventive method manufacturing.The both ends of capacitor element main body 10 are formed with and dispose the pair of external electrodes 4 of a plurality of interior electrode layer 3 conductings alternately in element body 10 inside.
Interior electrode layer 3 laminations are to the surface, both ends that each end face is exposed to alternately be opposite to capacitor element main body 10.Pair of external electrodes 4 be formed on the both ends of capacitor element main body 10 and be connected to mutual configuration interior electrode layer 3 expose end face, constitute capacitor circuit.
The shape of multilayer ceramic capacitor 1 or size can suitably determine that when being rectangular shape as capacitor 1, size is generally about long 0.6～3.2mm * wide 0.3～1.6mm * high 0.1～1.2mm according to purpose and purposes.
Composition the present invention for dielectric substance layer 2 does not do special qualification, as being made of following dielectric medium ceramic composition.The dielectric medium ceramic composition of the present embodiment preferably has the principal component that contains just like calcium titanate, strontium titanates and/or barium titanate etc., and has reducing resistance.
Except described principal component, also has the Mn oxide in the dielectric medium ceramic composition of the present embodiment as accessory ingredient.This is in order to give reducing resistance.Except this Mn oxide, can also contain more than one oxides in oxide of being selected from Sr, Y, Gd, Tb, Dy, V, Mo, Zn, Cd, Ti, Sn, W, Ba, Ca, Mg, Cr, Si and P etc. as accessory ingredient.
The composition example of dielectric substance layer 2 can be listed below scheme.
In the 1st scheme,, use to consist of [(Sr as principal component
1-xCa
x) O]
m(Ti
1-yZr
y) O
2The dielectric medium oxide.At this moment, x is generally 0 ≦ x ≦ 1.00, preferred 0.30 ≦ x ≦ 0.50; Y is generally 0 ≦ y ≦ 0.20, preferred 0 ≦ y ≦ 0.10; M is generally 0.94 ≦ m ≦ 1.02, preferred 0.97 ≦ m ≦ 1.015.With respect to this principal component, preferably contain the rare earth oxide that constitutes by Sc, Y and lanthanide series as accessory ingredient.More preferably, contain the oxide of the rare earth element of 0.02～2 mole (not containing 2 moles) with the rare earth element conversion with respect to 100 moles of principal components.Further, also can contain as accessory ingredient: be more than one materials in the oxide that is selected from V, Nb, W, Ta and Mo of 0.01～2 mole (not containing 2 moles) with respect to the content of 100 moles of principal components, and with respect to the content of 100 moles of principal components for the Mn oxide that is scaled 4 moles of less thaies with metallic element in the oxide and with respect to the content of 100 moles of principal components for be scaled the SiO that is selected from of 0～15 mole (not containing 0 mole and 15 moles) with oxide
2, MO (wherein M is at least a element that is selected among Ba, Ca, Sr and the Mg), Li
2O and B
2O
3More than one materials.
In the 2nd scheme,, use for example to consist of [(Ca as principal component
xSr
1-x) O]
m[(Ti
yZr
1-y) O
2] the dielectric medium oxide.At this moment, preferred x, y, m are 0 ≦ x ≦ 1,0 ≦ y ≦ 0.10,0.75 ≦ m ≦ 1.04.With respect to 100 moles of this principal components, contain preferably as accessory ingredient that to be converted into MnO be 0.2～5 mole Mn oxide, be converted into Al
2O
3Be the oxide of 0.1～10 mole Al, consist of [(Ba
zCa
1-z) O]
vSiO
2, wherein z and v are 0.5～15 mole of the composite oxides of 0 ≦ z ≦ 1,0.5 ≦ v ≦ 4.0.Being further used as the content that accessory ingredient can contain with respect to 100 moles of principal components is more than one materials of 0.02～1.5 mole the oxide that is selected from rare earth element, Nb, Mo, Ta and W.
In the 3rd scheme,, use to consist of [(Ca as principal component
1-xMe
x) O]
m(Zr
1-yTi
y) O
2, and Me is the dielectric medium oxide that is selected from more than one elements of Sr, Mg and Ba.At this moment, x is that 0 ≦ x ≦ 1.00, the preferred 0.1 ≦ y of y ≦ 0.8, m are generally 0.8 ≦ m ≦ 1.3, preferred 0.970 ≦ m ≦ 1.030.With respect to this principal component, preferably contain V oxide and Al oxide as accessory ingredient.More preferably with respect to 100 moles of principal components, contain and be converted into V
2O
5Be 0～7 mole (not containing 0 mole and 7 moles) the V oxide, be converted into Al
2O
3It is the Al oxide of 0～15 mole (not containing 0 mole and 15 moles).Further, the content that also can contain with respect to 100 moles of principal components as accessory ingredient is that the Mn element that is converted in the oxide is the Mn oxide of 0～5 mole (not containing 0 mole and 5 moles), with respect to the content of 100 moles of principal components for being converted into the SiO that is selected from that oxide is 0～20 mole (not containing 0 mole and 20 moles)
2, MO (wherein M is at least a element that is selected among Ba, Ca, Sr and the Mg), Li
2O and B
2O
3More than one materials, and the oxide of rare earth element.
Wherein, the composition of dielectric substance layer 2 of the present invention is not limited to above-mentioned scope.
The thickness of each dielectric substance layer 2 is in the present embodiment below the preferred 30 μ m.Count the present invention for the lamination of each dielectric substance layer 2 and do not do special qualification.As being the few lamination number about 10 layers, perhaps also can be preferred more than 50 layers, more preferably more than 100 layers, further preferred many lamination numbers more than 300 layers.
Contained electric conducting material can use cheap base metal in the interior electrode layer 3.Preferred nickel of base metal or nickel alloy.Nickel content in the alloy is preferably more than 90%.Can contain various micro constitutents such as phosphorus following about 0.1 weight %, iron, magnesium in nickel or the nickel alloy.The thickness of interior electrode layer 3 is below the 2 μ m in the present invention.
Material for outer electrode 4 is not done special qualification yet, uses copper or copper alloy, nickel or nickel alloy etc. usually, but can use silver or the silver and the alloy of palladium etc. yet.Thickness for outer electrode 4 is not done special qualification yet, but is generally about 10～50 μ m.
The manufacture method of a routine multilayer ceramic capacitor 1 in the present embodiment then, is described.
(1) at first, prepare dielectric substance layer with paste with behind sintering, will constitute the interior electrode layer paste of interior electrode layer 3 shown in Figure 1 through constituting dielectric substance layer 2 shown in Figure 1 behind the sintering.And preparation outer electrode paste.
Dielectric substance layer can be the organic system coating of dielectric medium raw material and organic carrier of having mixed with paste, also can be aqueous coating.
The dielectric medium raw material can be from by all cpds that forms composite oxides or oxide, as suitably selecting carbonate, nitrate, hydroxide, the organo-metallic compound etc., and mixes and use.
Organic carrier is the material of dissolved adhesive in organic solvent, does not do special qualification for the adhesive that is used for organic carrier, can suitably select from various common adhesives such as ethyl cellulose, polyvinyl butyral resin.Also have, also do not do special qualification, can suitably select from organic solvents such as the terpineol that is used for methods such as print process or thin plate method, butyl carbitol, acetone, toluene for the organic solvent that use this moment.
Also have, water soluble paint is the material that dissolves water-soluble binder, dispersant etc. in water, does not do special qualification for water-soluble binder, can suitably select from polyvinyl alcohol, cellulose, water soluble acrylic resin, emulsion etc.
The interior electrode layer paste is that the electric conducting material that will be made of above-mentioned various conductive metal or alloy or the various oxides that become above-mentioned electric conducting material behind sintering, organo-metallic compound, resinate etc. mix with above-mentioned organic carrier and modulate.
Outer electrode is also modulated with paste is identical with this interior electrode layer with paste.
Content for the organic carrier of each paste is not done special qualification, and content is usually, as adhesive be about 1～5 weight %, solvent is about 10～50 weight %.Also have, can contain the additive that is selected from various dispersants, plasticizer, dielectric medium, insulator etc. as required in each paste.
(2) then, use dielectric substance layer, make raw cook with paste and interior electrode layer paste.When using print process, the interior electrode layer of dielectric substance layer with paste and special adhesive is printed onto on the slide glass with the paste lamination, cut into given shape after, peel off from slide glass, as raw cook.When using the thin plate method, on slide glass, form the dielectric substance layer paste with specific thicknesses, to form raw cook, thereon with specific pattern print interior electrode layer with paste after, with its lamination as raw cook.
(3) then, the gained raw cook being carried out the unsticking mixture handles.It is with specific programming rate atmosphere temperature to be kept temperature from rise to the unsticking mixture as room temperature (25 ℃) that the unsticking mixture is handled, after this keeps temperature to keep special time, with the operation of specific cooling rate cooling.
In the present embodiment, preferred 5～300 ℃/hour of programming rate, more preferably 10～100 ℃/hour.The unsticking mixture keeps preferred 200～400 ℃ of temperature, and more preferably 250～350 ℃, this keeps preferred 0.5～24 hour of the retention time of temperature, more preferably 2～20 hours.Preferred 25～500 ℃/hour of cooling rate, more preferably 50～300 ℃/hour.
The preferred air of processing atmosphere or the reducing atmosphere of unsticking mixture.As the atmosphere gas in the reducing atmosphere preferably to as N
2And H
2Mist carry out humidification and use.If reduced by force, will exist reduce the tendency of unsticking mixture effect.
(4) then, the raw cook of sintering behind the unsticking mixture.Sintering is with specific programming rate atmosphere temperature to be kept temperature from rise to sintering as room temperature (25 ℃), after this keeps temperature to keep special time, reduces the operation of atmosphere temperature with specific cooling rate.
In the present embodiment, preferred 50～500 ℃/hour of programming rate, more preferably 100～300 ℃/hour.Sintering keeps preferred 1200～1350 ℃ of temperature, and more preferably 1200～1320 ℃, this keeps preferred 0.5～8 hour of the retention time of temperature, more preferably 1～3 hour.If sintering keeps temperature low excessively, this maintenance temperature hold-time even then extend, densification is also abundant inadequately, if too high, the deterioration of the capacity temperature characteristic that the diffusion that the interrupted phenomenon of electrode that the unusual sintering of interior electrode layer causes then takes place easily, constitutes the electric conducting material of interior electrode layer causes, constitute the phenomenons such as reduction of the dielectric medium ceramic composition of dielectric substance layer.Preferred 50～500 ℃/hour of cooling rate, more preferably 200～300 ℃/hour.
In the present embodiment, sintering carries out in reducing atmosphere.As the atmosphere gas in the reducing atmosphere preferably to as N
2And H
2Mist carry out humidification and use.Especially, during sintering at N
2N behind gas or the humidification
2After the maintenance temperature when being warming up to the unsticking mixture in the gas atmosphere, preferably change atmosphere and further continue to heat up, be cooled to after the 1st annealing keeps temperature T 1, preferably change N once more
2N behind gas or the humidification
2Gas atmosphere continues cooling.Partial pressure of oxygen in the sintering atmosphere preferred 6 * 10
-88～10
-4Pa.If partial pressure of oxygen is low excessively, then the electric conducting material of interior electrode layer will produce unusual sintering, cause intermittently, if too high, then have the tendency of interior electrode layer oxidation.
(5) then, the sheet sintered body behind the sintering is carried out annealing in process (heat treatment).Annealing is in order to reoxidize the processing of dielectric substance layer.
The characteristics of the present embodiment are that stage is carried out this annealing in process twice.That is, the annealing in process of the present embodiment has the 1st annealing operation and the 2nd annealing operation.
At first, as the 1st stage, the sheet sintered body behind sintering is carried out the 1st annealing in process (the 1st annealing operation).This operation mainly is to play the segregation that suppresses Mn, the effect of separating out.
The 1st annealing operation is as shown in Figure 2, with specific programming rate atmosphere temperature T0 is kept temperature T 1 from rise to the 1st annealing as room temperature (25 ℃), after keeping special time under this T1, with the operation of specific cooling rate cooling.
Programming rate is preferred 50～500 ℃/hour in the present embodiment, more preferably 100～300 ℃/hour.If programming rate is too fast, will there be the tendency of recurring structure defective (crackle), if slow excessively, the tendency of the poor flow that the Mn segregation causes then exist to take place.
The 1st annealing keeps temperature T 1 preferred 600～900 ℃, and more preferably 650～900 ℃, the retention time of this T1 is preferred below 6 hours, more preferably 2～5 hours.If T1 is low excessively, the then capacitor produced accelerated aging (=high-temperature load life-span) of insulation resistance that exists worsens, the tendency of reliability decrease, if too high, the tendency of then capacitor produced existence generation poor flow.If the retention time of T1 is long, by the tendency of capacitor produced existence generation poor flow.
Preferred 50～500 ℃/hour of cooling rate, more preferably 100～300 ℃/hour.
The preferred neutral atmosphere of the 1st annealing in process atmosphere.Atmosphere gas in the neutral atmosphere preferably uses as the N behind the humidification
2Gas.Can be during annealing at N
2After under the gas atmosphere atmosphere temperature being risen to the 1st annealing and keeps temperature T 1, change atmosphere, the N after also can adopting humidification in the overall process of the 1st annealing
2Gas atmosphere.Partial pressure of oxygen PO in the 1st annealing atmosphere
2Preferred 10
-7～0.1Pa.If partial pressure of oxygen is low excessively, the then capacitor produced tendency that has insulation resistance decline, life-span deterioration, if too high, the tendency of then capacitor produced existence generation poor flow.
In the 1st annealing operation, after described heating process and temperature keep operation, can be without cooling process, and forward aftermentioned the 2nd annealing operation to.
Then, as the 2nd stage, the sheet sintered body after the 1st annealing is carried out the 2nd annealing in process (the 2nd annealing operation).This operation is to be equivalent to the operation of annealing in process in the past, mainly is to play the effect that reoxidizes dielectric substance layer 2.Form the capacitor element main body 10 that constitutes by sintered body according to the 2nd annealing operation.
The 2nd annealing is as shown in Figure 2, with specific programming rate atmosphere temperature T0 is kept temperature T 2 from rise to the 2nd annealing as room temperature (25 ℃), after keeping special time under this T2, with the operation of specific cooling rate cooling.
Programming rate is preferred 50～500 ℃/hour in the present embodiment, more preferably 100～300 ℃/hour.If programming rate is too fast, will there be the tendency of recurring structure defective (crackle) in capacitor, if slow excessively, the tendency of the poor flow that the Mn segregation causes exist take place then.
The 2nd annealing keeps temperature T 2 preferred 900～1200 ℃ (not containing 900 ℃), and more preferably 950～1200 ℃, the retention time of this T2 is preferred below 6 hours, more preferably 2～5 hours.If T2 is low excessively, the then capacitor produced accelerated aging (high-temperature load life-span) that has an insulation resistance worsens, the tendency of reliability decrease, if too high, the tendency of capacitor produced existence generation poor flow.Especially it is higher more than 50 ℃ than described T1 to preferably set into T2, more preferably high more than 100 ℃.Poor (T2-T1) that be preferred described T2 and described T1 is more than 50 ℃, more preferably more than 100 ℃.By the difference that makes T1 and T2 is this degree, can further significantly improve effect of the present invention.If the retention time of this T2 is long, then there is the tendency that poor flow takes place in capacitor.
Preferred 50～500 ℃/hour of cooling rate, more preferably 100～300 ℃/hour.
The preferred neutral atmosphere of the 2nd annealing in process atmosphere.Atmosphere gas in the neutral atmosphere preferably uses as the N behind the humidification
2Gas.Can be during the 2nd annealing at N
2After under the gas atmosphere atmosphere temperature being risen to the 2nd annealing and keeps temperature T 2, change atmosphere, the N after also can adopting humidification in the overall process of the 2nd annealing
2Gas atmosphere.Partial pressure of oxygen PO in the 2nd annealing atmosphere
2Preferred 10
-5～10Pa.If partial pressure of oxygen is low excessively, then life of capacitors will worsen, if too high, then poor flow may take place capacitor.
Above-mentioned the 1st annealing and/or the 2nd annealing are respectively, and as shown in phantom in Figure 2, can only be made of temperature-rise period and temperature-fall period.That is, temperature hold-time can be zero, temperature might not be set keep operation.At this moment, the 1st～2 annealing keeps temperature T 1～2 and maximum temperature to have identical meanings.
In above-mentioned sintering circuit, can drop to the temperature identical to the atmosphere temperature of the cooling process of this sintering circuit with described temperature T 1, carry out described the 1st annealing operation, carry out described the 2nd annealing operation (with reference to Fig. 3) then.That is, sintering circuit be can follow and the 1st annealing operation and the 2nd annealing operation carried out continuously.
Also have, in the above-mentioned sintering circuit, after can dropping to the temperature (as about 100～500 ℃) that is lower than described temperature T 1 and is higher than room temperature to the atmosphere temperature of the cooling process of this sintering circuit, the rising atmosphere temperature, carry out described the 1st annealing operation, carry out described the 2nd annealing operation (with reference to Fig. 4) then.That is, sintering circuit be can follow and the 1st annealing operation and the 2nd annealing operation carried out continuously.
In the processing of above-mentioned unsticking mixture, sintering and the annealing operation, to N
2When carrying out humidification, gas or mist etc. can use as humidifier etc.At this moment, water temperature is preferably at 0～75 ℃.
(6) then, with as barreling or blasting treatment capacitor produced element body 10 being applied end surface grinding, printing or transfer printing outer electrode form outer electrode 4 with paste and sintering.Thus, obtain multilayer ceramic capacitor 1.Outer electrode uses the sintering condition of paste preferably as the N behind humidification
2Gas and H
2Kept about 10 minutes～1 hour at 600～800 ℃ in the mist of gas.Externally electrode 4 is surperficial by formation such as plating cover layer as required then.
It is first-class that the multilayer ceramic capacitor of making 1 will be installed to printed base plate according to scolding tin etc., is used for various e-machines etc.
Embodiment of the present invention more than has been described, but the present invention is not limited to these embodiments, can in the scope that does not break away from main idea of the present invention, implement various schemes.
For example, the multilayer ceramic capacitor 1 of having given an example in the above-mentioned embodiment is as multilayer ceramic electronic component, but the present invention is not limited thereto, and then can be arbitrary substance as long as have above-mentioned specific dielectric substance layer.
Also have, independently carry out the processing of unsticking mixture, sintering and annealing in the above-mentioned embodiment separately, but the present invention is not limited thereto, also can carry out two or more at least operations continuously.When carrying out continuously, preferably after the unsticking mixture is handled, do not cool off and change atmosphere, then be warming up to sintering and keep temperature to carry out sintering, then cooling reaches and changes atmosphere when the 1st annealing keeps temperature T 1 and anneal.
Embodiment
Then, further specialize the embodiment of embodiment of the present invention for example, further describe the present invention.But the present invention is not limited to these embodiment.
Sample according to sequentially built multilayer ceramic capacitor shown below.
The modulation of each paste
At first, following making dielectric substance layer paste.
As the initiation material of making dielectric material, prepare the principal component raw material (SrCO of average grain diameter 0.1～1 μ m separately
3, CaCO
3, TiO
2, ZrO
2) and accessory ingredient raw material (V
2O
5, Al
2O
3, MnCO
3, BaCO
3, CaCO
3, SiO
2Deng).
Then, consist of following proportioning principal component raw material and accessory ingredient raw material weighing and after being mixed into sintering, obtain the dielectric medium raw material by drying.
Sample 1～3 fits in 100 moles of [(Ca
0.6Sr
0.4) O] (Zr
0.1Ti
0.9) O
2+ 0.1 mole V
2O
5(the SiO of+1 mole MnO+2 mole
2+ CaO)+0.5 mole Y
2O
3
Sample 4～6 and sample 10～29 fit in 100 moles of [(Ca
0.6Sr
0.4) O] (Zr
0.5Ti
0.5) O
2+ 0.1 mole V
2O
5+ 0.5 mole Al
2O
3(the Ba of+1 mole MnO+2 mole
0.6Ca
0.4) SiO
2(being called BCG).
Sample 7～9 fits in 100 moles of [(Ca
0.6Sr
0.4) O] (Zr
0.9Ti
0.1) O
2+ 0.3 mole Al
2O
3The BCG of+1 mole MnO+2.5 mole.
BCG is by BaCO
3, CaCO
3And SiO
2With ball mill wet mixed 16 hours, after the drying, sintering in 1000～1300 ℃ of air was further made with the ball mill case of wet attrition in 100 hours.
Gained dielectric medium raw material 100 weight portions, acrylic resin 4.8 weight portions, carrene 40 weight portions, trichloroethanes 20 weight portions, Mineral spirits 6 weight portions and acetone 4 weight portions are mixed with ball mill, make paste.
Then, following making interior electrode layer paste.With triple-roller mill mix Ni particle 100 weight portions, organic carrier (ethyl cellulose resin 8 weight portions being dissolved into the material that forms in butyl carbitol 92 weight portions) 40 weight portions and butyl carbitol 10 weight portions of average grain diameter 0.3 μ m, make paste.
Then, following making outer electrode paste.Cu particle 100 weight portions of the average grain diameter of mixing 0.5 μ m, organic carrier (ethyl cellulose resin 8 weight portions being dissolved into the material that forms in butyl carbitol 92 weight portions) 35 weight portions and butyl carbitol 7 weight portions are made paste.
The making of raw cook
Then, use above-mentioned dielectric substance layer on the PET film, to form the raw cook of thickness 10 μ m with paste, thereon with specific pattern print interior electrode layer with paste after, peel off raw cook from the PET film.
Then, these raw cooks of lamination and protection are pushed and are obtained raw cook with raw cook (not printing the raw cook of interior electrode layer with paste).Lamination number with thin plate of internal electrode is decided to be 100 layers.
Then, raw cook is cut into specific dimensions, carry out unsticking mixture operation, sintering circuit, the 1st annealing and the 2nd annealing, obtain the multilayer ceramic sintered body.
The unsticking mixture is handled
Programming rate: 50 ℃/hour
Keep temperature: 280 ℃
Retention time: 8 hours
Atmosphere: in the air
Cooling rate: 50 ℃/hour
Cooling temperature: room temperature (25 ℃)
Sintering
Programming rate: 200 ℃/hour
Keep temperature: 1250 ℃
Retention time: 2 hours
Atmosphere: the mixed-gas atmosphere (H of nitrogen behind the humidification and hydrogen
2: 5 volume %, partial pressure of oxygen=10
-6Pa)
Cooling rate: 300 ℃/hour
Cooling temperature: room temperature (25 ℃)
The 1st annealing
Programming rate: 200 ℃/hour
Keep temperature T 1: with reference to each table
Retention time: 2 hours
Atmosphere: (partial pressure of oxygen=10 of the nitrogen behind the humidification
-4Pa)
Cooling rate: 200 ℃/hour
Cooling temperature: room temperature (25 ℃)
The 2nd annealing
Programming rate: 200 ℃/hour
Keep temperature T 2: with reference to each table
Retention time: 2 hours
Atmosphere: (partial pressure of oxygen=10 of the nitrogen behind the humidification
-3Pa)
Cooling rate: 200 ℃/hour
Cooling temperature: room temperature (25 ℃)
In the cooling process of sintering circuit, finish cooling process for sample 24 when atmosphere temperature drops to T1, enter the 1st annealing operation, implement the 2nd annealing (with reference to Fig. 3) then.
In the cooling process of sintering circuit, atmosphere temperature drops to when the temperature that is lower than T1 and is higher than room temperature is 300 ℃ and finishes cooling process for sample 25, and the atmosphere temperature that raises then enters the 1st annealing operation, implements the 2nd annealing (with reference to Fig. 4) then.
The humidification of the atmosphere gas when sintering, the 1st sintering and the 2nd sintering uses the humidifier of 20 ℃ of water temperatures.
Then, end face with sand-blast grinding lamination ceramic sintered bodies is transferred to end face to outer electrode with paste, under the mixed-gas atmosphere of nitrogen behind the humidification and hydrogen, form outer electrode in 10 minutes at 800 ℃ of sintering, obtain the multilayer ceramic capacitor sample of formation shown in Figure 1.
Capacitor produced specimen size is long 1.6mm * wide 0.8mm * high 0.8mm, and the number that is clipped in two dielectric substance layers between the interior electrode layer is 40, and its thickness is 7 μ m, and the thickness of interior electrode layer is 1.2 μ m.
The evaluation of characteristic
The high-temperature load life-span (HALT) of the capacitor produced sample of each self-evaluation, dielectric absorption (tan δ), fault of construction (poor flow rate).Show the result in table 1～2.
The high-temperature load life-span (HALT) is to measure by the capacitor sample being remained on the direct voltage that applies 50V/ μ m under 200 ℃.This high-temperature load life-span is that 10 capacitor samples are measured, and its average life time estimates by measuring.As evaluation, the high-temperature load life-span is the characteristic that is even more important when dielectric substance layer is carried out thin layer, being the life-span from applying the timing definition that begins to drop to resistance one digit number.Good being decided to be more than 1000 hours.
Dielectric absorption (tan δ, unit are %) is to the capacitor sample, counts (YHP company makes 4274A) with digital LCR down for 25 ℃ in fiducial temperature, measures under the condition of frequency 1MHz, input signal level (mensuration voltage) 1Vrms.As evaluation, tan δ is decided to be when following good 0.01%.The value of tan δ is to be obtained by the mean value that the sample that uses capacitor is counted n=10 the value of measuring.
For fault of construction (poor flow rate) is at first to the capacitor sample, count (YHP company makes 4274A) with digital LCR down for 25 ℃ in fiducial temperature, under the condition of frequency 1MHz, input signal level (mensuration voltage) 1Vrms, measure the static capacity of n=150.The average also sample of low 5% above static capacity than n=150 is carried out resin fill grinding, the goods that internal electrode and outer electrode are not connected are decided to be fault of construction product (poor flow product).As evaluation, the situation of disqualification rate 0% is decided to be well.
Table 1
| Sample | The 1st annealing T1 (℃) | The 1st annealing PO 2(Pa) | The 2nd annealing T2 (℃) | The 2nd annealing PO 2(Pa) | The high-temperature load life-span (hr) | tanδ (％ ) | Poor flow rate (%) | |
| 1 | Comparative example | 700 | 1.0E-05 | — | — | 302 | 0.58 | 0 |
| 2 | Comparative example | 1000 | 1.0E-01 | — | — | 1053 | 0.01 | 4.4 |
| 3 | Embodiment | 700 | 1.0E-05 | 1000℃ | 1.0E-01 | 1289 | 0.01 | 0 |
| 4 | Comparative example | 700 | 1.0E-05 | — | — | 532 | 0.44 | 0 |
| 5 | Comparative example | 1000 | 1.0E-01 | — | — | 1177 | 0.01 | 3.7 |
| 6 | Embodiment | 700 | 1.0E-05 | 1000℃ | 1.0E-01 | 1350 | 0.01 | 0 |
| 7 | Comparative example | 700 | 1.0E-05 | — | — | 719 | 0.31 | 0 |
| 8 | Comparative example | 1000 | 1.0E-01 | — | — | 1245 | 0.01 | 3.1 |
| 9 | Embodiment | 700 | 1.0E-05 | 1000℃ | 1.0E-01 | 1430 | 0.01 | 0 |
Table 2
| Sample | Classification | The 1st annealing T1 (℃) | The 1st annealing PO 2(Pa) | The 2nd annealing T2 (℃) | The 2nd annealing PO 2(Pa) | The high-temperature load life-span (hr) | tanδ (％ ) | Poor flow rate (%) |
| 10 | Reference example | 500 | 1.0E-07 | 800 | 1.0E-04 | 787 | 0.33 | 0 |
| 11 | Reference example | 500 | 1.0E-07 | 1000 | 1.0E-01 | 1031 | 0.11 | 0 |
| 12 | Reference example | 500 | 1.0E-07 | 1300 | 1.0E+01 | 1398 | 0.01 | 5.4 |
| 13 | Embodiment | 600 | 1.0E-06 | 1000 | 1.0E-01 | 1244 | 0.01 | 0 |
| 14 | Comparative example | 700 | 1.0E-05 | 600 | 1.0E-06 | 693 | 0.24 | 0 |
| 15 | Reference example | 700 | 1.0E-05 | 800 | 1.0E-04 | 842 | 0.19 | 0 |
| 16 | Embodiment | 700 | 1.0E-05 | 900 | 1.0E-02 | 1188 | 0.01 | 0 |
| 17 | Embodiment | 700 | 1.0E-05 | 950 | 5.0E-02 | 1212 | 0.01 | 0 |
| 6 | Embodiment | 700 | 1.0E-05 | 1000 | 1.0E-01 | 1350 | 0.01 | 0 |
| 18 | Reference example | 700 | 1.0E-05 | 1300 | 1.0E+01 | 1455 | 0.01 | 6.4 |
| 19 | Embodiment | 900 | 1.0E-02 | 950 | 5.0E-02 | 1024 | 0.01 | 0 |
| 20 | Embodiment | 900 | 1.0E-02 | 1000 | 1.0E-01 | 1384 | 0.01 | 0 |
| 21 | Comparative example | 1300 | 1.0E+01 | 800 | 1.0E-04 | 1484 | 0.01 | 6.3 |
| 22 | Comparative example | 1300 | 1.0E+01 | 1000 | 1.0E-01 | 1549 | 0.01 | 6.5 |
| 23 | Comparative example | 1300 | 1.0E+01 | 1300 | 1.0E+01 | 1592 | 0.01 | 7.2 |
| 24 | Embodiment | 700 | 1.0E-05 | 1000 | 1.0E-01 | 1050 | 0.01 | 0 |
| 25 | Embodiment | 700 | 1.0E-05 | 1000 | 1.0E-01 | 1200 | 0.01 | 0 |
Table 3
| Sample | Classification | The 1st annealing T1 (℃) | The 1st annealing PO 2(Pa) | The 2nd annealing T2 (℃) | The 2nd annealing PO 2(Pa) | The high-temperature load life-span (hr) | tanδ (％ ) | Poor flow rate (%) |
| 26 | Reference example | 600 | 1.0E-08 | 1000 | 1.0E-01 | 1003 | 0.01 | 3.5 |
| 6 | Embodiment | 700 | 1.0E-05 | 1000 | 1.0E-01 | 1350 | 0.01 | 0 |
| 27 | Reference example | 900 | 9.8E+00 | 1000 | 1.0E-01 | 1438 | 0.01 | 5.3 |
| 28 | Reference example | 700 | 1.0E-05 | 900 | 1.0E-06 | 849 | 0.10 | 0 |
| 29 | Reference example | 700 | 1.0E-05 | 1200 | 9.8E+02 | 1321 | 0.01 | 1.9 |
As shown in table 1, no matter the composition of dielectric substance layer is how, the situation of carrying out annealing in process according to two stages is, the HALT height, and tan δ is low, and the poor flow rate is 0% (sample 3,6,9).With respect to this, the situation of only carrying out 1 annealing in process is, can confirm that there is the tendency that worsens among HALT, the tan δ and poor flow rate at least.
As shown in table 2, when the maintenance temperature T 1～2 of the 1st～2 annealing is in the scope of the invention, the HALT height, tan δ is low, and the poor flow rate is 0% (sample 13,16,17,19,20,24,25).With respect to this, keep temperature T 1～2 to be in the scope of the invention when outer, can confirm that there is the tendency that worsens among HALT, the tan δ and poor flow rate at least.
As shown in table 3, even the maintenance temperature T 1～2 of the 1st～2 annealing is in the scope of the invention, but by changing the processing atmosphere (partial pressure of oxygen) in each annealing operation, various characteristics is shown as and is affected.
Claims (5)
1. the manufacture method of a multilayer ceramic electronic component, it is characterized in that: have a plurality of dielectric substance layers of the mutual configuration of sintering with paste and contain the base metal interior electrode layer with the sintering circuit of the laminate of paste, the laminate of the laminate behind this sintering after 600～900 ℃ temperature T is carried out the 1st annealing operation of annealing in process for 1 time and annealed the 1st at 900～1200 ℃ but do not contain the 2nd annealing operation that 900 ℃ temperature T is carried out annealing in process for 2 times, wherein, described dielectric substance layer has to contain with paste and consists of [(Sr
1-xCa
x) O]
m(Ti
1-yZr
y) O
2, wherein x is that 0 ≦ x ≦ 1.00, y are that 0 ≦ y ≦ 1.00, m are the principal component raw material and the accessory ingredient raw material that contains Mn of the dielectric medium oxide of 0.75 ≦ m ≦ 1.3, the difference T2-T1 of described T2 and described T1 is more than 50 ℃.
2. the manufacture method of multilayer ceramic electronic component as claimed in claim 1, it is characterized in that: the described atmosphere temperature of cooling process that keeps temperature to reduce the described sintering circuit of atmosphere temperature from sintering is reduced to the temperature identical with described temperature T 1, carry out described the 1st annealing operation, carry out described the 2nd annealing operation then.
3. the manufacture method of multilayer ceramic electronic component as claimed in claim 1 is characterized in that: in described first annealing operation, to the programming rate of described temperature T 1 be 50～500 ℃/hour.
4. the manufacture method of multilayer ceramic electronic component as claimed in claim 1 is characterized in that: in described second annealing operation, to the programming rate of described temperature T 2 be 50～500 ℃/hour.
5. the manufacture method of multilayer ceramic electronic component as claimed in claim 1, it is characterized in that: described the 1st annealing operation is 10
-7Carry out under the partial pressure of oxygen of～0.1Pa, described the 2nd annealing operation is 10
-5Carry out under the partial pressure of oxygen of～10Pa.
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|---|---|---|---|
| JP2003373494 | 2003-10-31 | ||
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