CN1765824A - Dielectric ceramic composition and electronic device - Google Patents
Dielectric ceramic composition and electronic device Download PDFInfo
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- CN1765824A CN1765824A CN 200510113296 CN200510113296A CN1765824A CN 1765824 A CN1765824 A CN 1765824A CN 200510113296 CN200510113296 CN 200510113296 CN 200510113296 A CN200510113296 A CN 200510113296A CN 1765824 A CN1765824 A CN 1765824A
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Abstract
A dielectric ceramic composition, comprising a main component including barium titanate; a first subcomponent including at least one kind selected from MgO, CaO, BaO and SrO; a second subcomponent functioning as a sintering auxiliary agent; a third subcomponent including at least one kind selected from V 2 O 5 , MoO 3 and WO 3 ; a fourth subcomponent including an oxide of R1, wherein R1 is at least one kind selected from Sc, Er, Tm Yb and Lu ; a fifth subcomponent including CaZrO 3 or CaO + ZrO 2 ; and an eighth subcomponent including an oxide of A, wherein A is at least one kind selected from a cation element group having an effective ionic radius at the time of 6 coordination of 0.065 nm to 0.085 nm ; wherein a ratio of the eighth subcomponent with respect to 100 moles of the main component is 0 to 4 moles, wherein 0 mole and 4 moles are excluded, and the value is in terms of an A oxide.
Description
Technical field
The present invention relates to have the dielectric ceramic composition of reducing resistance and used the multi-layer ceramic capacitor (Plot Layer セ ラ ミ Star Network コ Application デ Application サ of this dielectric ceramic composition) etc. electronic unit.
Background technology
To multi-layer ceramic capacitor as electronic unit, except requiring the specific inductivity height, the life-span of insulation resistance IR is long, and DC bias characteristic good (specific inductivity through time with low uncertainty) in addition, also require temperature profile good, particularly require under the condition of strictness temperature profile smooth according to purposes.In recent years, in carrying various electronic installations such as engine electronic control unit (ECU) in motor car engine, crankshaft angle sensor, ABS (Anti-lock Braking System) (ABS) module, use multi-layer ceramic capacitor gradually.Because these electronic installations are used for stably carrying out engine control, drive control and braking control, therefore, require the temperature stability of circuit good.
The environment that estimate to use these electronic installations is that the winter temperature in cold drops to below-20 ℃, in addition, behind engine starting, rise at summer temp+more than 130 ℃.The trend of cutting down the distribution that connects electronic installation and its controlled member equipment is arranged recently, also electronic installation is arranged on outside the car sometimes, therefore, concerning electronic installation, its environment is more and more harsher.Thereby the electrical condenser that just need be used for these electronic installations is smooth in wide temperature range temperature profile.Specifically, need temperature characteristics of capacitance not only to satisfy the X7R characteristic (55 ℃～125 ℃, Δ C/C=± 15% in) of EIA standard, also will satisfy the dielectric ceramic composition of the X8R characteristic (55 ℃～150 ℃, Δ C/C=± 15% in) of EIA standard.
As the dielectric ceramic composition that satisfies the X8R characteristic, several motions are arranged.
Open Japanese kokai publication hei 10-25157 communique, spy and to have proposed in the flat 9-40465 communique with BaTiO
3In the dielectric ceramic composition for principal constituent, in order to satisfy the X8R characteristic, by replacing BaTiO with Bi, Pb etc.
3In Ba, Curie temperature is offset to high temperature side.In addition, also proposed by selecting BaTiO
3+ CaZrO
3+ ZnO+Nb
2O
5The composition of system satisfies X8R characteristic (spy open flat 4-295048 communique, spy open flat 4-292458 communique, spy are opened flat 4-292459 communique, the spy opens flat 5-109319 communique and the flat 6-243721 communique of Te Kai).
But in these composition systems, all owing to using volatile Pb, Bi and Zn, therefore, prerequisite is a sintering in oxidizing atmospheres such as air.Therefore, have and in the internal electrode of electrical condenser, to use cheap base metals such as Ni, and must use the problem of high price precious metals such as Pd, Au and Ag.
To this, for make the specific inductivity height, satisfy the X8R characteristic, can be in reducing atmosphere sintering, the applicant has proposed dielectric ceramic composition shown below (spy opens the 2000-154057 communique).This spy opens the dielectric ceramic composition of putting down in writing in the 2000-154057 communique to have at least: principal constituent is BaTiO
3Comprise and be selected from MgO, CaO, BaO, SrO and Cr
2O
3In the first at least a minor component; With (Ba, Ca)
xSiO
2+xSecond minor component of (wherein, x=0.8～1.2) expression; Comprise and be selected from V
2O
5, MoO
3And WO
3In the 3rd at least a minor component; The oxide compound that comprises R1 (wherein, R1 is selected from least a among Sc, Er, Tm, Yb and the Lu) the fourth officer composition, each minor component with respect to the ratio of 100 moles of principal constituents is, first minor component: 0.1～3 mole, second minor component: 2～10 moles, the 3rd minor component: 0.01～0.5 mole, fourth officer composition: 0.5～7 mole (wherein, the mole number of fourth officer composition is the independent ratio of R1).
In addition, the applicant has proposed dielectric ceramic composition shown below (spy opens the 2001-192264 communique).This spy opens the dielectric ceramic composition of putting down in writing in the 2001-192264 communique to have at least: the principal constituent that comprises barium titanate; Comprise and be selected from MgO, CaO, BaO, SrO and Cr
2O
3In the first at least a minor component; Contain silicon oxide as principal constituent second minor component; Comprise and be selected from V
2O
5, MoO
3And WO
3In the 3rd at least a minor component; The fourth officer composition that comprises the oxide compound (wherein, R1 is selected from least a among Sc, Er, Tm, Yb and the Lu) of R1; Comprise CaZrO
3Or CaO+ZrO
3The 5th minor component, each minor component with respect to the ratio of 100 moles of principal constituents is, first minor component: 0.1～3 mole, second minor component: 2～10 moles, the 3rd minor component: 0.01～0.5 mole, fourth officer composition: 0.5～7 mole (wherein, the mole number of fourth officer composition is the independent ratio of R1), the 5th minor component: 0＜the 5th minor component≤5 mole.
In arbitrary application of above-mentioned the applicant, first minor component such as MgO with respect to the ratio of 100 moles of principal constituents all be 0.1 mole or more than.
In addition, the applicant has proposed dielectric ceramic composition shown below (spy opens the 2002-255639 communique).This spy opens the dielectric ceramic composition of putting down in writing in the 2002-255639 communique to have: the principal constituent that comprises barium titanate; First minor component that comprises the oxide compound (wherein, AE is selected from least a among Mg, Ca, Ba and the Sr) of AE; The oxide compound that comprises R (wherein, R is selected from least a among Y, Dy, Ho and the Er) second minor component, each minor component with respect to the ratio of 100 moles of principal constituents is first minor component: 0 mole＜first minor component＜0.1 mole, second minor component: 1 mole＜second minor component＜7 mole.
Open the technology that 2000-154057 communique, spy are opened 2001-192264 communique and Te Kai 2002-255639 communique according to the applicant's above-mentioned spy, can improve specific inductivity really, satisfy the X8R characteristic, and can be in reducing atmosphere sintering.
But, though satisfied the X8R characteristic, sometimes from room temperature to pyritous IR temperature dependency variation, become difficulty as the actual use of product.
Summary of the invention
The object of the present invention is to provide a kind of specific inductivity height, the life-span that can keep insulation resistance, temperature characteristics of capacitance satisfy the EIA standard X8R characteristic (55～150 ℃, Δ C/C=± 15% in), can in reducing atmosphere, carry out sintering, simultaneously, improved the temperature dependent dielectric ceramic composition of IR.In addition, the object of the present invention is to provide and a kind ofly can use such dielectric ceramic composition to realize small-sized and high capacity, particularly corresponding to the electronic units such as multi-layer ceramic capacitor of thin-layer and small-sizeization.
In order to achieve the above object, according to first viewpoint of the present invention, provide a kind of dielectric ceramic composition, said composition contains:
The principal constituent that comprises barium titanate;
Comprise the first at least a minor component that is selected among MgO, CaO, BaO and the SrO;
Second minor component as sintering aid;
Comprise and be selected from V
2O
5, MoO
3And WO
3In the 3rd at least a minor component;
The fourth officer composition that comprises the oxide compound (wherein, R1 is selected from least a among Sc, Er, Tm, Yb and the Lu) of R1;
Comprise CaZrO
3Or CaO+ZrO
2The 5th minor component;
The 8th minor component that comprises the oxide compound (wherein, A is that the effective ionic radius when being selected from 6 coordinations (6 coordination) is at least a in the cation element group of 0.065nm～0.085nm) of A,
Above-mentioned the 8th minor component is 0～4 mole (wherein, not comprising 0 mole and 4 moles, is the value that is converted into the A oxide compound) with respect to the ratio of 100 moles of above-mentioned principal constituents.
In first viewpoint, the above-mentioned A in the oxide compound that comprises in above-mentioned the 8th minor component preferably is selected from least a in Al, Cr, Ga, the Ge cation element group.
In first viewpoint, each minor component with respect to the ratio of 100 moles of above-mentioned principal constituents preferably,
First minor component: 0.1～3 mole,
Second minor component: 2～10 moles,
The 3rd minor component: 0.01～0.5 mole,
The fourth officer composition: 0.5～7 mole (wherein, the mole number of fourth officer composition is the independent ratio of R1),
The 5th minor component: 0＜the 5th minor component≤5 mole.
In first viewpoint, the oxide compound that further preferably comprises R2 (wherein, R2 is selected from least a among Y, Dy, Ho, Tb, Gd and the Eu) as the 6th minor component, with respect to 100 moles of the principal constituents that comprises barium titanate, the content of the 6th minor component is 9 moles or following (wherein, the mole number of the 6th minor component is the independent ratio of R2).
In first viewpoint, with respect to 100 moles of the principal constituents that comprises barium titanate, the total content of fourth officer composition and the 6th minor component is 13 moles or following (wherein, the mole number of fourth officer composition and the 6th minor component is the independent ratio of R1 and R2) preferably.
In first viewpoint, above-mentioned second minor component preferably is selected from SiO
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 at least a represented compound.Second minor component plays sintering aid.
In above-mentioned the 5th minor component, the mol ratio of Ca and Zr is arbitrarily, but preferred Ca/Zr=0.5～1.5, more preferably Ca/Zr=0.8～1.5, further preferred Ca/Zr=0.9～1.1.
In first viewpoint, further preferably have MnO as the 7th minor component, with respect to 100 moles of the principal constituents that comprises barium titanate, the content of above-mentioned the 7th minor component be 0.5 mole or below.
Perhaps, according to second viewpoint of the present invention, provide a kind of dielectric ceramic composition, this dielectric ceramic composition contains:
The principal constituent that comprises barium titanate;
First minor component that comprises MgO;
Second minor component as sintering aid;
Comprise and be selected from V
2O
5, MoO
3And WO
3In the 3rd at least a minor component;
The fourth officer composition that comprises the oxide compound (wherein, R1 is selected from least a among Sc, Er, Tm, Yb and the Lu) of R1;
Comprise CaZrO
3Or CaO+ZrO
2The 5th minor component;
Comprise MnO or Cr
2O
3The 7th minor component;
Comprise Al
2O
3The 8th minor component,
Above-mentioned first minor component, the 7th minor component, the 8th minor component with respect to the ratio of 100 moles of above-mentioned principal constituents be,
First minor component: 0.2～0.75 mole,
The 7th minor component: 0.1～0.3 mole (wherein, the mole number of the 7th minor component is the ratio that converts by Mn element or Cr element),
The 8th minor component: 0.5～4 mole (wherein, not comprising 4 moles),
The Mn element that comprises in Mg element that comprises in above-mentioned first minor component and above-mentioned the 7th minor component, the mol ratio of Cr element have the relation of 0.3≤(Mn+Cr)/Mg≤0.5.
The maximum of second viewpoint is characterised in that, must comprise as the MgO of first minor component with as the Al of the 8th minor component
2O
3, simultaneously, will be as the content of the MgO of first minor component and MnO or Cr as the 7th minor component
2O
3Content be set at above-mentioned relation.
In second viewpoint, above-mentioned second～the 5th minor component with respect to the ratio of 100 moles of above-mentioned principal constituents preferably,
Second minor component: 2～10 moles,
The 3rd minor component: 0.01～0.5 mole,
The fourth officer composition: 0.5～7 mole (wherein, the mole number of fourth officer composition is the independent ratio of R1),
The 5th minor component: 0＜the 5th minor component≤5 mole.
In second viewpoint, the oxide compound that further preferably has a R2 (wherein, R2 is selected from least a among Y, Dy, Ho, Tb, Gd and the Eu) as the 6th minor component, with respect to 100 moles of the principal constituents that comprises barium titanate, the content of above-mentioned the 6th minor component is 9 moles or following (wherein, the mole number of the 6th minor component is the independent ratio of R2).
In second viewpoint, with respect to 100 moles of the principal constituents that comprises barium titanate, the total content of fourth officer composition and the 6th minor component is 13 moles or following (wherein, the mole number of fourth officer composition and the 6th minor component is the independent ratio of R1 and R2) preferably.
In second viewpoint, preferred above-mentioned first minor component further comprises one or more compounds that are selected among CaO, BaO and the SrO.
In second viewpoint, preferred above-mentioned second minor component is to be selected from SiO
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 at least a represented compound.
The electronic unit that first viewpoint of the present invention and second viewpoint relate to is so long as have the electronic unit of dielectric layer, and no particular determination for example, has the multi-layer ceramic capacitor of the common alternately laminated capacitor element main body of dielectric layer and interior electrode layer.In the present invention, above-mentioned dielectric layer is made of any dielectric ceramic composition that relates in above-mentioned first viewpoint or second viewpoint.As the electro-conductive material that comprises in the interior electrode layer, no particular determination for example is Ni or Ni alloy.
Electronic unit as first viewpoint of the present invention and second viewpoint relate to specifically exemplifies multi-layer ceramic capacitor, piezoelectric element, chip inductor, type piezoresistor, slice heat sensitive resistor, plate resistor and other surface mount chip type electronic unit (SMD) etc.
In addition, the ionic radius of putting down in writing in this specification sheets is based on the value of document " R.D.Shannon, ActaCrystallogr., A32,751 (1976) ".
The inventor can improve found that the temperature dependent element-specific group of IR studies to not influencing purpose temperature profile (X8R characteristic), the cation element group that effective ionic radius during 6 coordinations enters into pre-determined range is effective, has finished the present invention's (invention that first viewpoint relates to) based on this discovery.
" IR temperature dependency " is the index of understanding fully how insulation resistance IR changes with respect to temperature variation.This IR temperature dependency can be estimated with respect to the ratio that IR changed (velocity of variation) under the reference temperature (for example, room temperature is 25 ℃) by the IR that calculates under the preset temperature (for example 150 ℃).IR velocity of variation between a plurality of temperature is more little, and then can being judged as IR, gradually to spend dependency just good more, otherwise velocity of variation is big more, and the IR temperature dependency is just poor more.Even the temperature profile of electrostatic capacitance has satisfied the X8R of EIA standard, if the IR temperature dependency of (particularly from the room temperature to high temperature) is poor in the temperature range of X8R, as the actual use of the product difficulty that just becomes.
In the present invention,, exemplified room temperature (25 ℃) and high temperature (150 ℃), insulation resistance at each temperature is being made as IR as a plurality of temperature
25, IR
150The time, by calculating the size of " IR gives up the throne (IR purlin fall Chi) " shown in the following formula 1, estimate the temperature dependent quality of IR.
Log (IR
150/ IR
25) ... formula 1
In the present invention, form, add the 8th minor component that constitutes by the element-specific group for the high dielectric medium that also can satisfy the X8R characteristic of specific inductivity.Therefore, the dielectric ceramic composition that the present invention relates to is when satisfying the X8R characteristic, and the IR temperature dependency from room temperature (25 ℃) to high-temperature portion (150 ℃) is little.Specifically, can make the IR shown in the above-mentioned formula 1 give up the throne-2.00 or more than.
The dielectric ceramic composition that the present invention relates to, because specific inductivity height, temperature characteristics of capacitance satisfy the X8R characteristic of EIA standard, therefore, used the electronic units such as ceramic chip capacitor of dielectric ceramic composition of the present invention in the environment that is exposed to the sun as motor car engine etc. at high temperature, also can be suitable for.
In addition, the dielectric ceramic composition that the present invention relates to does not contain elements such as volatile Pb, Bi, Zn.Therefore, can in reducing atmosphere, carry out sintering.
Promptly, according to the present invention, X8R characteristic that a kind of specific inductivity height, the life-span that can keep insulation resistance, temperature characteristics of capacitance satisfy the EIA standard can be provided, can in reducing atmosphere, carry out sintering, simultaneously, improve the temperature dependent dielectric ceramic composition of IR.
When using dielectric ceramic composition of the present invention to make electronic unit such as ceramic chip capacitor, can use base metals such as Ni and Ni alloy as internal electrode, realize the low cost of electronic unit.And, even sintered dielectric ceramic composition in reducing atmosphere, the electronic unit that obtains also satisfies the X8R characteristic, apply DC electric field and the electric capacity aging property that produce also good (=electric capacity through the time change little), the deterioration of insulation resistance is little, and reliability is also good.
Promptly, electronic units such as multi-layer ceramic capacitor with the dielectric layer that constitutes by dielectric ceramic composition of the present invention, stably work in the various device that can under the such harsh and unforgiving environments of the electronic installation that resembles automobile, use, can significantly improve the reliability of suitable device.
According to above content, can expect that also dielectric medium of the present invention forms the means that the high-temperature area rate of temperature change as the thin layerization that suppresses to be accompanied by dielectric layer worsens and play effect.
In addition, the insulation resistance life-span of the dielectric ceramic composition that the present invention relates to is long, and in addition, DC bias characteristic (volts DS of specific inductivity applies dependency) and TC bias characteristic (temperature characteristics of capacitance when applying volts DS) are stable.Particularly confirmed by adding the 8th minor component the significantly improving of TC bias characteristic.
In addition, the dielectric ceramic composition that the present invention relates to is not owing to contain objectionable impuritiess such as Pb, Bi, and therefore, the discarded and processing after the use etc. are little to the influence of environment.
Therefore, the dielectric ceramic composition of the application of the invention just provides the electronic units such as multi-layer ceramic capacitor with good characteristic easily.In addition,,, also can satisfy the X8R characteristic even make the dielectric layer thin layerization if use the dielectric ceramic composition that the present invention relates to, and, can prevent effectively that the life-span of insulation resistance from reducing.Thereby, can in electronic units such as multi-layer ceramic capacitor, realize small-sized and high capacity, particularly further talk about easily and answer thin-layer and small-sizeization.Therefore, with regard to the easier high density integrated circuit having that is installed to.
In existing dielectric ceramic composition, be accompanied by the thin layerization of the dielectric layer of each layer, have the particularly trend of the temperature characteristics of capacitance deterioration of high temperature side.That is, the percentage of capacitance variation with temperature curve of high temperature side has towards clockwise trend.To this, according to the present invention, the percentage of capacitance variation with temperature curve that can make high temperature side is towards counterclockwise direction.If in the electronic unit that has satisfied the X7R characteristic, use this phenomenon, just can further realize the thin layerization of each layer dielectric layer than prior art.
In addition, in the invention that second viewpoint relates to, must contain Al
2O
3As the 8th minor component, with the content of the MgO that must contain in first minor component with comprise MnO or Cr
2O
3The ratio of content of the 7th minor component be set at the scope of regulation, that is, the Mn element, the Cr element that comprise in Mg element that comprises in first minor component and the 7th minor component are counted in molar ratio, are set in the scope of 0.3≤(Mn+Cr)/Mg≤0.5.Therefore, except above-mentioned each effect, can also realize the improvement of high temperature accelerated aging.
Description of drawings
Below, describe embodiments of the present invention in detail based on accompanying drawing.Wherein,
Fig. 1 is the sectional view of the multi-layer ceramic capacitor that relates to of an embodiment of the invention.
Fig. 2 A is the photo of Mg elements segregation state in the dielectric layer of the embodiment that shows that the present invention's second viewpoint relates to, and Fig. 2 B is the photo that shows Mg elements segregation state in the dielectric layer that comparative example relates to.
Fig. 3 A is the photo of Mn elements segregation state in the dielectric layer of the embodiment that shows that the present invention's second viewpoint relates to, and Fig. 3 B is the photo that shows Mn elements segregation state in the dielectric layer that comparative example relates to.
Embodiment
First embodiment
Below first embodiment of the present invention is described.
In the first embodiment,, enumerate multi-layer ceramic capacitor shown in Figure 1, its structure and manufacture method are described as electronic unit.
Multi-layer ceramic capacitor
As shown in Figure 1, the multi-layer ceramic capacitor 1 of the electronic unit that relates to as first embodiment has had dielectric layer 2 alternately laminated and the capacitor element main body 10 of interior electrode layer 3.Formed pair of external electrodes 4 at the two ends of capacitor element main body 10, this outer electrode 4 and each interior electrode layer 3 conducting in the inside of element body 10 alternately configured.Interior electrode layer 3 alternately carries out stacked in the mode that two end surfaces of capacitor element main body 10 opposite faces expose with each end face.Pair of external electrodes 4 is formed on the two ends of capacitor element main body 10, is connected with the end face that exposes of the interior electrode layer 3 of alternately configured, constitutes capacitor circuit.
Profile and size to capacitor element main body 10 do not have particular restriction, can suitably set according to purposes, usually can configuration file roughly be rectangular shape, size normally long (0.4～5.6mm) * wide (0.2～5.0mm) * high (about 0.2～1.9mm).
Dielectric layer
The dielectric ceramic composition that the present invention's first viewpoint relates to has:
Comprise barium titanate and (preferably use composition formula Ba
mTiO
2+mExpression, m is 0.995≤m≤1.010, Ba is 0.995≤Ba/Ti≤1.010 with the ratio of Ti) principal constituent;
Comprise and be selected from first at least a among MgO, CaO, BaO and the SrO minor component:
Second minor component as sintering aid:
Comprise and be selected from V
2O
5, MoO
3And WO
3In the 3rd at least a minor component:
The fourth officer composition that comprises the oxide compound (wherein, R1 is selected from least a among Sc, Er, Tm, Yb and the Lu) of R1;
Comprise CaZrO
3Or CaO+ZrO
2The 5th minor component:
The 8th minor component that comprises the oxide compound (wherein, A is that the effective ionic radius when being selected from 6 coordinations is at least a in the cation element group of 0.065nm～0.085nm) of A.
The 8th minor component influences temperature characteristics of capacitance hardly, has the temperature dependent effect of the IR of improvement.In first viewpoint of the present invention, it is characterized in that, form for the dielectric medium that satisfies the X8R characteristic, it is measured in accordance with regulations contain the 8th minor component that constitutes by specific element set.
The cation element group of above-mentioned the 8th minor component comprises I (0.067nm), Ge (0.067nm), Al (0.0675mm), Cu (0.068nm), Fe (0.069nm), Ni (0.070nm), Au (0.071nm), As (0.072nm), Cr (0.0755nm), Ga (0.076nm), At (0.076nm), Os (0.077nm), Nb (0.078nm), Ta (0.078nm), Co (0.079nm), Rh (0.080nm), Ir (0.082nm), Ru (0.082nm), Sn (0.083nm), but does not comprise P (0.052nm), K (0.152nm).Effective ionic radius during numeral 6 coordinations in the bracket, below identical.
In the above-mentioned cation element group, the effective ionic radius when preferably using 6 coordinations is the element of 0.067～0.076nm.Comprise I, Ge, Al, Cu, Fe, Ni, Au, As, Cr, Ga, At in these preferred elements groups, more preferably use to be selected from least a in Al, Cr, Ga, the Ge cation element group, further preferably use Al at least.Under situation about being used in combination more than 2 kinds or 2 kinds, particularly preferred combination is Al+Cr, Al+Ga, Al+Ge.
With respect to 100 moles of above-mentioned principal constituents, the content of the 8th minor component is 0～4 mole (wherein not comprising 0 mole and 4 moles) by the value that changes the A oxide compound into, preferably 0～3.5 mole (wherein not comprising 0 mole), more preferably 0.5～3.5 mole, further preferred 1～2 mole, preferred especially 1～1.5 mole.If the content of the 8th minor component is very few, IR is temperature dependent, and to improve effect just insufficient.On the other hand, if content is too much, the trend that just has temperature characteristics of capacitance to worsen.Particularly find to surpass 1 mole the 8th minor component by adding, the TC bias characteristic significantly improves.
The above-mentioned ratio of the 8th minor component is not the independent mol ratio of A, but the mol ratio of A oxide compound.That is, for example under the situation of the oxide compound that has used Al as the 8th minor component, the ratio of the 8th minor component is 1 mole, and this is not meant that the ratio of Al is 1 mole, and is meant Al
2O
3Ratio be 1 mole.
In addition, under the situation of multiple element (oxide compound) as the 8th minor component of using more than 2 kinds or 2 kinds, with respect to 100 moles of above-mentioned principal constituents, its total content gets final product in above-mentioned scope.That is, the composition ratio of each oxide compound is any in the 8th minor component.
Above-mentioned each minor component is BaTiO with respect to principal constituent
3Ratio be, for 100 moles of BaTiO
3,
First minor component: 0.1～3 mole,
Second minor component: 2～10 moles,
The 3rd minor component: 0.01～0.5 mole,
The fourth officer composition: 0.5～7 mole,
The 5th minor component: 0＜the 5th minor component≤5 mole,
Preferably
First minor component: 0.5～2.5 mole,
Second minor component: 2.0～5.0 moles,
The 3rd minor component: 0.1～0.4 mole,
The fourth officer composition: 0.5～5.0 mole,
The 5th minor component: 0.5～3 mole.
The above-mentioned ratio of fourth officer composition is not the mol ratio of R1 oxide compound, but the independent mol ratio of R1.That is, for example using under the situation of oxide compound as the fourth officer composition of Yb, the ratio of fourth officer composition is 1 mole, and this is not meant Yb
2O
3Ratio be 1 mole, and be meant that the ratio of Yb is 1 mole.
In this manual, represented to constitute each oxide compound of principal constituent and each minor component with stoichiometric composition, but the state of oxidation of each oxide compound can nonstoichiometry be formed also.Wherein, the amount of metal that comprises from the oxide compound that constitutes each minor component oxide compound that is converted into above-mentioned stoichiometric composition is tried to achieve the above-mentioned ratio of each minor component.
By containing above-mentioned the first～five minor component, just can both keep high-k, satisfy the X8R characteristic again.The preferred content of first～the 5th minor component and the reasons are as follows.
First minor component (MgO, CaO, BaO and SrO) shows the effect of the temperature characteristics of capacitance planarization of sening as an envoy to.If the content of first minor component is very few, it is big that percentage of capacitance variation with temperature just becomes.On the other hand, if content is too much, then coking property worsens.In addition, the composition ratio of each oxide compound is any in first minor component.
Second minor component is the minor component as sintering aid.As compound, can preferably use by being selected from SiO with such sintering aid function
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 at least a represented compound.Second minor component like this except effect with sintering aid, the effect of the disqualification rate of initial insulation resistance when improving thin layer in addition.If the content of second minor component is very few, then temperature characteristics of capacitance is with regard to variation, and in addition, IR (insulation resistance) is low.On the other hand, if content is too much, then the IR life-span just inadequately, the rapid reduction of specific inductivity occurs.
More preferably above-mentioned second minor component as (Ba, Ca)
xSiO
2+xShown in (wherein, x=0.7～1.2).As the more preferably form of second minor component [(Ba, Ca)
xSiO
2+x] in BaO and CaO, be also contained in first minor component, but because composite oxides (Ba, Ca)
xSiO
2+xFusing point is low, thus good for the reactivity of principal constituent, therefore, in the present invention, preferably add BaO and/or CaO with the form of above-mentioned composite oxides.As the more preferably mode of second minor component (Ba, Ca)
xSiO
2+xIn x, preferably 0.7～1.2, more preferably 0.8～1.1.If x is too small, i.e. SiO
2Too much, just with the BaTiO of principal constituent
3Reaction worsens dielectric characteristic.On the other hand, if x is excessive, then, coking property is worsened, so bad because fusing point uprises.In addition, the ratio of Ba and Ca is arbitrarily, also can only contain wherein a kind of.
The 3rd minor component (V
2O
5, MoO
3And WO
3) show the effect of the above temperature characteristics of capacitance planarization of Curie temperature of sening as an envoy to and improve the effect in IR life-span.If the content of the 3rd minor component is very few, then such effect is just insufficient.On the other hand, if content is too much, IR just significantly reduces.In addition, the composition ratio of each oxide compound is any in the 3rd minor component.
Fourth officer composition (R1 oxide compound) shows the effect and the effect that make temperature characteristics of capacitance planarization of Curie temperature to the high temperature side skew of sening as an envoy to.If the content of fourth officer composition is very few, then such effect is insufficient, and temperature characteristics of capacitance is with regard to variation.On the other hand, if content is too much, the trend that then has coking property to worsen.In the fourth officer composition, improve the high and cheap aspect of effect from characteristic and consider, preferred Yb oxide compound.
The 5th minor component (CaZrO
3) show that the Curie temperature of sening as an envoy to is to high temperature side effect that is offset and the effect that makes the temperature characteristics of capacitance planarization.Improve the effect of CR long-pending (CR Plot) and D.C. isolation strength at break in addition in addition.But if the content of the 5th minor component is too much, then the IR accelerated aging significantly worsens, and temperature characteristics of capacitance (X8R characteristic) is with regard to variation.To CaZrO
3The interpolation form do not have particular determination, can exemplify oxide compound, CaCO that CaO etc. is made of Ca
3Deng carbonate, organic compound, CaZrO
3Deng.Ratio to Ca and Zr does not have particular determination, and fixing on and not being solid-solubilized in principal constituent is BaTiO
3In degree get final product but the mol ratio of Ca and Zr (Ca/Zr) preferably 0.5～1.5, more preferably 0.8～1.5, further preferred 0.9～1.1.
By adjusting fourth officer composition (R1 oxide compound) and the 5th minor component (CaZrO
3) content, can make temperature characteristics of capacitance (X8R characteristic) planarization, it is long-pending to improve high temperature accelerated aging and CR.Particularly in above-mentioned numerical range, can suppress separating out of out-phase, realize the homogenizing of tissue.If the content of fourth officer composition is too much, then huge needle-like crystal is that pyrrhite (バ イ ロ Network ロ ア) is just separated out mutually easily, when the thickness attenuation that makes between the dielectric layer of multi-layer ceramic capacitor, finds significant deterioration in characteristics (minimizing that CR is long-pending).On the other hand, if the content of fourth officer composition is very few, just can not satisfy temperature characteristics of capacitance.If the content of the 5th minor component is too much, then improve the long-pending and direct current disintegration voltage VB of CR, but the temperature characteristics of capacitance deterioration, the IR accelerated aging is variation also.
In the dielectric ceramic composition that first viewpoint relates to, as required, the R2 oxide compound (wherein, R2 is selected from least a among Y, Dy, Ho, Tb, Gd and the Eu) that preferably contains (more preferably 0.5～9 mole) below 9 moles or 9 moles is as the 6th minor component.The 6th minor component (R2 oxide compound) demonstrates and improves the IR and the effect in IR life-span, and is also few to the detrimentally affect of temperature characteristics of capacitance.But, if the content of R2 oxide compound is too much, the trend that just has coking property to worsen.In the 6th minor component, improve the high and cheap aspect consideration of effect, preferred Y oxide compound from characteristic.
With respect to principal constituent BaTiO
3100 moles, the total content of fourth officer composition and the 6th minor component be preferably 13 moles or below, further preferred 10 moles or following (wherein, the mole number of fourth officer composition and the 6th minor component is the independent ratio of R1 and R2).Be used to guarantee that coking property is good.
In addition, in the dielectric ceramic composition that first viewpoint relates to, also can contain MnO as the 7th minor component.The 7th minor component demonstrates the effect of acceleration of sintering, the effect that improves IR and the effect in raising IR life-span.In order fully to obtain such effect, the 7th minor component is with respect to BaTiO
3100 moles ratio preferably 0.01 mole or more than.But, if the content of the 7th minor component is too much, just temperature characteristics of capacitance is brought detrimentally affect, thus be preferably 0.5 mole or below.
In addition, under Ba in the principal constituent that constitutes perovskite structure with at least a displacement among Sr, Zr and the Sn and the situation of Ti, owing to Curie temperature is offset to low temperature side, so the temperature characteristics of capacitance variation more than 125 ℃.Therefore, preferably do not use the BaTiO that comprises these elements
3(for example (Ba, Sr) TiO
3) as principal constituent.But, if the level (all about 0.1 mole of % of dielectric ceramic composition is following) that contains as impurity does not just have special problem.
The average crystalline particle diameter of the dielectric ceramic composition that first viewpoint is related to does not have particular determination, can be according to dielectric layer thickness etc., and suitably decision from the scope of for example 0.1～3 μ m.
Temperature characteristics of capacitance has thin more deterioration more of dielectric layer and the more little trend that worsens more of average crystal particle diameter.Therefore, dielectric ceramic composition of the present invention specifically, is effective especially under the situation of 0.1～0.5 μ m at the average crystalline particle diameter under the situation that must reduce the average crystalline particle diameter.In addition, if reduce the average crystalline particle diameter, then the IR life-span just elongated, in addition, the electric capacity under the DC electric field through the time tail off, therefore, from this point, preferably the average crystalline particle diameter is as described above little.
Can be by select forming the Curie temperature (from the transformation temperature of ferroelectrics) that changes the dielectric ceramic composition that first viewpoint relates to, but in order to satisfy the X8R characteristic to paraelectrics, preferably 120 ℃ or more than, more preferably 123 ℃ or more than.In addition, can utilize DSC (differential scanning calorimetric measurement) to wait and measure Curie temperature.
Dielectric layer thickness one deck that the dielectric ceramic composition that is related to by first viewpoint constitutes is generally 40 μ m or following, in particular for 30 μ m or following.The lower limit of thickness is 0.5 μ m normally.
The dielectric ceramic composition that first viewpoint relates to is effective for the improvement of the temperature characteristics of capacitance of the multi-layer ceramic capacitor with the dielectric layer after such thin layerization.In addition, the stacked number of dielectric layer normally about 2～300.
Used the multi-layer ceramic capacitor of the dielectric ceramic composition that first viewpoint relates to, be suitable for as at the equipment electronic unit that more than 80 ℃, particularly uses under 125～150 ℃ the environment.And in such temperature range, the temperature profile of electric capacity satisfies the R characteristic of EIA standard, and also satisfies the X8R characteristic.In addition, also can satisfy the B characteristic [in 25～85 ℃ rate of change of capacitance ± 10% with interior (20 ℃ of reference temperatures)] of EIAJ standard and the X7R characteristic of EIA standard (55～125 ℃, Δ C=± 15% in) simultaneously.
And, for example, room temperature (25 ℃) and high temperature (150 ℃) insulation resistance at each temperature are being made as IR
25And IR
150The time, " IR gives up the throne " that can make 1 expression of following formula-2.00 or more than.That is, the IR temperature dependency is little.
Log (IR
150/ IR
25) ... formula 1
In multi-layer ceramic capacitor, dielectric layer is applied more than the 0.02V/ μ m usually, particularly more than the 0.2V/ μ m, further be more than the 0.5V/ μ m, the alternating-electric field that general is below about 5V/ μ m and with its DC electric field below the eclipsed 5V/ μ m, even but applying such electric field, the temperature profile of electric capacity is also stable.
Interior electrode layer
The electro-conductive material that contains in the interior electrode layer 3 is not had particular determination, but, therefore, can use base metal because the constituent material of dielectric layer 2 has reducing resistance.As the base metal of electro-conductive material use, preferably Ni or Ni alloy.As the Ni alloy, preferably be selected from one or more elements among Mn, Cr, Co and the Al and the alloy of Ni, the Ni content in the alloy preferably 95 weight % or more than.
In addition, also can comprise the following various trace ingredientss such as P of about 0.1 weight % in Ni or the Ni alloy.
Can be according to the suitable thickness of decision interior electrode layer such as purposes, but 0.5～5 μ m normally, about preferred especially 0.5～2.5 μ m.
Outer electrode
The electro-conductive material that contains in the external electrode layer 4 is not had particular determination, but in the present embodiment, can use cheap Ni, Cu and their alloy.
Can be according to the suitable thickness of decision external electrode layer such as purposes, but usually preferably about 10～50 μ m.
The manufacture method of multi-layer ceramic capacitor
Used the multi-layer ceramic capacitor and the existing multi-layer ceramic capacitor of the dielectric ceramic composition that the present invention's first viewpoint relates to same, the print process and the diaphragm method (シ one ト method) of the routine by using thickener are made base substrate (グ リ one Application チ Star プ), behind its sintering, make by printing or transfer printing outer electrode and sintering.Below manufacture method is specifically described.
At first, prepare dielectric layer, its coatingization is modulated into the dielectric layer thickener with the dielectric ceramic composition powder that comprises in the thickener.
Dielectric layer can be the mixing organic coating that obtains of dielectric ceramic composition powder and organic carrier with thickener, also can be aqueous coating.
As the dielectric ceramic composition powder, can use above-mentioned oxide compound and its mixture, composite oxides, but in addition, also can mix use and become all cpds of above-mentioned oxide compound or composite oxides, for example the material of from carbonate, oxalate, nitrate, oxyhydroxide, organometallic compound etc., suitably selecting by sintering.Decide the content of each compound in the dielectric ceramic composition powder according to the amount of the composition that becomes above-mentioned dielectric ceramic composition behind the sintering.
Under the state before making coating, the particle diameter of dielectric ceramic composition powder is normally about median size 0.1～3 μ m.
Organic carrier (PVC ヒ Network Le) is that binding agent is dissolved in material in the organic solvent.The binding agent that is used for organic carrier is not had particular determination, can from conventional various binding agents such as ethyl cellulose, polyvinyl butyral acetal, suitably select.In addition, the organic solvent of use is particular determination not also, can suitably select from various organic solvents such as Terpineol 350, diethylene glycol monobutyl ether, acetone, toluene according to the method for utilizing print process and diaphragm method etc.
In addition, dielectric layer is being made with thickener under the situation of aqueous coating, can water system carrier and dielectric medium raw material that water miscible binding agent and dispersion agent etc. are dissolved in the water is mixing.The water-soluble binder that is used for the water system carrier is not had particular determination, for example use polyvinyl alcohol, Mierocrystalline cellulose, water soluble acrylic resin etc.
Interior electrode layer becomes various oxide compounds, organometallic compound, resinate of above-mentioned electro-conductive material etc. after by the electro-conductive material that will be made of above-mentioned various conductive metal or alloy or sintering with thickener, mixing and prepare with above-mentioned organic carrier.
Outer electrode can similarly prepare with above-mentioned paste for internal electrode with thickener.
Content for the organic carrier in above-mentioned each thickener is not made particular restriction, is that common content gets final product, and for example binding agent is about 1～5 weight %, and solvent is about 10～50 weight %.In addition, also can in each thickener, contain the additive that is selected from various dispersion agents, softening agent, dielectric medium, the isolator etc. as required.Their total content is preferably at 10 weight % or following.
Coming with under the situation of print process, dielectric layer folded on the substrates such as being printed on PET with paste layers with thickener and interior electrode layer, cut into the regulation shape after, from strippable substrate, become the base substrate.
In addition, under the situation of using the diaphragm method, use dielectric layer to form base sheet (グ リ one ソ シ one ト) with thickener, print in the above interior electrode layer with thickener after, with its stacked base substrate that becomes.
Before sintering, the base substrate is implemented to take off adhesive treatment.Can suitably determine to take off adhesive treatment according to the kind of electro-conductive material in the interior electrode layer thickener, but use under the situations of base metal as electro-conductive material such as Ni or Ni alloy that preferably the oxygen partial pressure that will take off in the binding agent atmosphere is made as 10
-45～10
5Pa.Oxygen partial pressure is if not enough above-mentioned scope is taken off the just reduction of binding agent effect.In addition, oxygen partial pressure just has the trend of interior electrode layer oxidation if surpass above-mentioned scope.
In addition, as the binding agent condition of taking off in addition, preferably heat-up rate is made as 5～300 ℃/hour, further preferred 10～100 ℃/hour, to keep temperature to be made as 180～400 ℃, further preferred 200～350 ℃, temperature hold-time was made as 0.5～24 hour further preferred 2～20 hours.In addition, sintering atmosphere preferably is made as air or reducing atmosphere, as the atmosphere gas in the reducing atmosphere, preferably with for example N
2And H
2The mixed gas humidification after use.
Atmosphere gas in the time of can suitably determining base substrate sintering with the kind of the electro-conductive material in the thickener according to interior electrode layer, but using under the situations of base metal as electro-conductive material such as Ni or Ni alloy, the oxygen partial pressure in the sintering atmosphere gas preferably is made as 10
-7～10
-3Pa.If the not enough above-mentioned scope of oxygen partial pressure, cause the unusual sintering of electro-conductive material of interior electrode layer sometimes and rupture.In addition, if oxygen partial pressure surpasses above-mentioned scope, the trend of interior electrode layer oxidation is just arranged.
In addition, preferably 1100～1400 ℃ of the maintenance temperature during sintering, further preferred 1200～1380 ℃, more preferably 1260～1360 ℃.If keep the not enough above-mentioned scope of temperature, densification is just insufficient, if surpass above-mentioned scope, just be easy to generate because the temperature characteristics of capacitance that the diffusion of the lead rupture that the unusual sintering of interior electrode layer causes, interior electrode layer constituent material causes worsens, dielectric ceramic composition easily is reduced.
As sintering condition in addition, preferably heat-up rate is made as 50～500 ℃/hour, further preferred 200～300 ℃/hour, preferably temperature hold-time is made as 0.5～8 hour, further preferred 1～3 hour, preferably speed of cooling is made as 50～500 ℃/hour, further preferred 200～300 ℃/hour.In addition, sintering atmosphere is preferably reducing atmosphere, as the gas in the atmosphere, preferably with for example N
2And H
2The mixed gas humidification after use.
In reducing atmosphere, under the agglomerating situation, preferably the capacitor element main body is implemented annealing.Annealing is in order to reoxidize the processing of dielectric layer, because like this can the phenomenal growth IR life-span, so the reliability raising.
Oxygen partial pressure in the annealing atmosphere preferably more than 0.1Pa, preferred especially 0.1～10Pa.If the not enough above-mentioned scope of oxygen partial pressure, reoxidizing of dielectric layer is just difficult, if surpass above-mentioned scope, the trend of interior electrode layer oxidation is just arranged.
Maintenance temperature during annealing is preferably below 1100 ℃, preferred especially 500～1100 ℃.Because if keep the not enough above-mentioned scope of temperature, the oxidation of dielectric layer is just insufficient, therefore, the IR step-down, in addition, the IR life-span just shortens easily.On the other hand, if keep temperature to surpass above-mentioned scope, then not only internal electrode oxidation, electric capacity reduce, and internal electrode and dielectric medium reaction, just are easy to generate that temperature characteristics of capacitance worsens, IR reduction, IR life-span reduce.In addition, annealing also can only be made of temperature-rise period and temperature-fall period.That is, also temperature hold-time can be made as zero.Under this situation, keep temperature and top temperature equivalent in meaning.
As annealing conditions in addition, preferably temperature hold-time is made as 0～20 hour, further preferred 2～10 hours, speed of cooling is made as 50～500 ℃/hour, further preferred 100～300 ℃/hour.In addition, as the gas in the annealing atmosphere, preferably use the N behind the humidification for example
2Gas etc.
Above-mentioned taking off in adhesive treatment, sintering and the annealing, can use for example humidification N such as humidifier
2Gas or mixed gas etc..Under this situation, preferably 5～75 ℃ of water temperatures.
Taking off adhesive treatment, sintering and annealing can carry out continuously, also can independently carry out.Under the situation of carrying out continuously, preferably to take off and do not cool off after the adhesive treatment and change atmosphere gas, the maintenance temperature when continuing to be warmed up to sintering is carried out sintering, and then cooling when reaching annealed and keep temperature, changes atmosphere gas and anneals.On the other hand, under the situation of independently carrying out, preferably when sintering, at N
2The N of gas or humidification
2Change atmosphere gas after being warmed up to maintenance temperature when taking off adhesive treatment under the gas atmosphere, further continue then to heat up, also preferably after the maintenance temperature when being cooled to anneal, become N once more
2The N of gas or humidification
2Gas atmosphere is proceeded cooling.In addition, can be when annealing, at N
2Be warmed up under the gas atmosphere and keep changing atmosphere gas after the temperature, also can be with the whole process of annealed all at the N of humidification
2Carry out in the gas atmosphere.
To the capacitor element main body that obtains as mentioned above, utilize for example tumbling polishing and sandblast cleaning etc. to implement end surface grinding, printing or transfer printing external electrode layer form outer electrode 4 with thickener and sintering.As external electrode layer with the sintering condition of thickener, the N behind humidification preferably for example
2With H
2Mixed gas in 600～800 ℃, carry out about 10 minutes～1 hour.Then, as required, by forming coating on the surface of electroplate waiting electrode 4 externally.
The multi-layer ceramic capacitor of the present embodiment that will make like this by soldering etc. is installed on the printed base plate, is used for various electronicss etc.
Second embodiment
Below second embodiment of the present invention is described.
In second embodiment with first embodiment similarly, as electronic unit, exemplified multi-layer ceramic capacitor shown in Figure 11, its structure and manufacture method are described.
The difference of second embodiment and first embodiment is that dielectric layer 2 contains the dielectric ceramic composition that second viewpoint relates to.
The maximum that the dielectric ceramic composition that second viewpoint relates to has is characterised in that, must comprise respectively as the MgO of first minor component with as the Al of the 8th minor component
2O
3, simultaneously, will be as the content of the MgO of first minor component and MnO and Cr as the 7th minor component
2O
3Content be set at above-mentioned relation.
In addition, in the following description, omitted and the explanation partly of the first embodiment multiple, only distinct portions has been described.
Dielectric layer
The dielectric ceramic composition that second viewpoint of the present invention relates to has:
Comprise barium titanate and (preferably use composition formula Ba
mTiO
2+mExpression, wherein m is 0.995≤m≤1.010, Ba is 0.995≤Ba/Ti≤1.010 with the ratio of Ti) principal constituent;
First minor component that comprises MgO;
Second minor component as sintering aid;
Comprise and be selected from V
2O
5, MoO
3And WO
3In the 3rd at least a minor component;
The fourth officer composition that comprises the oxide compound (wherein, R1 is selected from least a among Sc, Er, Tm, Yb and the Lu) of R1;
Comprise CaZrO
3Or GaO+ZrO
2The 5th minor component;
Comprise MnO or Cr
2O
3The 7th minor component;
Comprise Al
2O
3The 8th minor component.
The 8th minor component influences temperature characteristics of capacitance hardly, has the temperature dependent effect of the IR of improvement.In second embodiment, form for the dielectric medium that satisfies the X8R characteristic, make it measure in accordance with regulations to contain and comprise Al
2O
3The 8th minor component.
With respect to 100 moles of above-mentioned principal constituents, the content of the 8th minor component is pressed Al
2O
3Conversion is 0.5～4 mole (wherein not comprising 4 moles), preferably 0.5～3.5 mole (wherein not comprising 0 mole), more preferably 1～2 mole, further preferred 1～1.5 mole.If the content of the 8th minor component is very few, it is just insufficient to improve the temperature dependent effect of IR.On the other hand, if content is too much, the trend that just has temperature characteristics of capacitance to worsen.
The maximum that the dielectric ceramic composition that second viewpoint relates to has is characterised in that, except the 8th minor component of afore mentioned rules amount, first minor component and the 7th minor component that contain specified amount, and, with the content of the MgO that must contain in first minor component with comprise MnO or Cr
2O
3The content of the 7th minor component be set at the relation of regulation.By being set at such composition, the additive effect that just can both keep the 8th minor component is the temperature dependent effect of improving of IR, can improve the high temperature accelerated aging again.
First minor component (MgO is necessary, and GaO, BaO and SrO are any) shows the effect of the temperature characteristics of capacitance planarization of sening as an envoy to.Particularly the MgO that must contain in first minor component also has effect that makes the raising of high temperature accelerated aging and the effect that the TC bias characteristic is improved.With respect to 100 moles of above-mentioned principal constituents, it is 0.2～0.75 mole that the content of first minor component converts by each oxide compound, preferably 0.3～0.7 mole, and more preferably 0.35～0.5 mole.If the content of first minor component is very few, then percentage of capacitance variation with temperature just becomes big, the trend that has the high temperature accelerated aging to worsen.On the other hand, if content is too much, then the high temperature accelerated aging just worsens.In addition, CaO, BaO, SrO are compositions arbitrarily, can add as required.
The 7th minor component (MnO or Cr
2O
3) show that the reducing resistance of sening as an envoy to improves, suppress effect and the effect of raising IR and the effect that the high temperature accelerated aging is improved of the semiconductor transformation of dielectric layer.With respect to 100 moles of principal constituents, it is 0.1～0.3 mole that the content of the 7th minor component converts by Mn element or Cr element, preferably 0.15～0.3 mole, and more preferably 0.2～0.25 mole.If the content of the 7th minor component is very few, the trend of dielectric layer semiconductor transformation is just arranged.On the other hand, if content is too much, temperature characteristics of capacitance just worsens sometimes.
In addition, as the Cr of the 7th minor component
2O
3, owing to constitute Cr
2O
36 coordinations of Cr element the time effective ionic radius be the scope of 0.065nm～0.085nm, therefore, belong to the 8th minor component in the above-described first embodiment, but in second embodiment, be used as the 7th minor component.That is, in second embodiment, with Cr
2O
3The above-mentioned effect that is had (raising of reducing resistance, the inhibition of the semiconductor transformation of dielectric layer, the raising of IR, the raising of high temperature accelerated aging) is the starting point, has added Cr
2O
3, this point is different with first embodiment.
And, in the dielectric ceramic composition that second viewpoint of the present invention relates to, the content of first minor component and the content of the 7th minor component are set at above-mentioned scope, and, with the content of the MgO that must contain in first minor component with comprise MnO or Cr
2O
3The content of the 7th minor component be set at the relation of regulation.That is, control is as the content of the MgO of first minor component with as the MnO or the Cr of the 7th minor component
2O
3Content, making the Mn element that comprises in the Mg element that comprises in first minor component and the 7th minor component, the mol ratio of Cr element is the scope of 0.3≤(Mn+Cr)/Mg≤0.5.By content and the 7th minor component (MnO or Cr with MgO
2O
3) content be set at such relation, just can improve MnO or Cr fully as the 7th minor component
2O
3Additive effect.
If (Mn+Cr)/Mg is set in outside the above-mentioned scope MgO and the 7th minor component (MnO or Cr
2O
3) additive effect just insufficient, the high temperature accelerated aging just worsens.In addition, as the inadequate reason of additive effect of such MgO and the 7th minor component, think because by adding the 8th minor component Al
2O
3, MgO and the 7th minor component (MnO or Cr
2O
3) in dielectric layer, produce segregation.
To this, in second viewpoint,, just prevented the segregation of MgO and the 7th minor component effectively by (Mn+Cr)/Mg is set at the afore mentioned rules scope, brought into play the additive effect of these MgO and the 7th minor component fully, the high temperature accelerated aging is improved.In addition, do not using Cr as the 7th minor component
2O
3Situation under, in fact do not contain the Cr element in the dielectric ceramic composition.Therefore, under this situation, (Mn+Cr)/Mg in fact just is equivalent to Mn/Mg.Perhaps, under the situation of not using MnO, in fact do not contain the Mn element in the dielectric ceramic composition, (Mn+Cr)/Mg in fact just is equivalent to Cr/Mg.
Minor component except the first, the 7th, the 8th above-mentioned minor component, be that the ratio of above-mentioned second～the 5th minor component can be identical with above-mentioned first embodiment.By containing second～the 5th minor component, can keep high specific inductivity and satisfy the X8R characteristic.
In addition, in the dielectric ceramic composition that second viewpoint relates to, preferably contain R2 oxide compound (wherein, R2 is selected from least a among Y, Dy, Ho, Tb, Gd and the Eu) as required as the 6th minor component.The ratio of the 6th minor component can be identical with above-mentioned first embodiment.
In the dielectric ceramic composition that second viewpoint relates to, add the Al that comprises of specified amount
2O
3The 8th minor component, simultaneously, with the content of the MgO that must contain in first minor component with comprise MnO or Cr
2O
3The ratio of content of the 7th minor component be set at the scope of afore mentioned rules.Therefore, in the effect of above-mentioned first embodiment, also have the effect that can improve the high temperature accelerated aging.
In addition, the multi-layer ceramic capacitor that relates to of second embodiment can be made with the method identical with above-mentioned first embodiment.
More than be illustrated about embodiments of the present invention, but the present invention is not limited to these embodiments, can implement various modes in the scope that does not break away from purport of the present invention.
For example, in the above-described embodiment, as the electronic unit that the present invention relates to, exemplified multi-layer ceramic capacitor, but as the electronic unit that the present invention relates to, being not limited to multi-layer ceramic capacitor, also can be any element with the dielectric layer that is made of the above-mentioned dielectric ceramic composition of forming.
Embodiment
Exemplify the embodiment that has further specialized embodiments of the present invention below, the present invention is described in further detail.But, the invention is not restricted to these embodiment.
Below, embodiment 1,2 and comparative example 1 are the embodiment that first viewpoint of the present invention relates to.
At first, as the starting raw material that is used to make dielectric substance, prepared the principal constituent raw material (BaTiO of median size 0.1～1 μ m respectively
3) and first～the 8th minor component raw material.
The raw material of MgO and MnO uses carbonate (first minor component: MgCO
3, the 7th minor component: MnCO
3), other raw materials use oxide compound (second minor component: (Ba
0.6Ca
0.4) SiO
3, the 3rd minor component: V
2O
5, fourth officer composition: Yb
2O
3, the 5th minor component: CaZr
3, the 6th minor component: Y
2O
3, the 8th minor component: Al
2O
3).By utilizing ball mill with BaCO
3, CaCO
3And SiO
2Wet-mixed 16 hours, dry back sintering in 1150 ℃ of air utilized the ball mill wet pulverization 100 hours again, prepared the second minor component (Ba
0.6Ca
0.4) SiO
3In addition, by utilizing ball mill with CaCO
3And ZrO
3Wet-mixed 16 hours, sintering in dry back 1150 ℃ of air utilizes ball mill to pulverize again 24 hours, prepares the 5th minor component CaZrO
3
Distinguish weighing BaCO in addition
3And TiO
2, used the ball mill wet-mixed about 16 hours, after being dried, sintering in the air of 1100 ℃ of temperature, then by ball mill its with about 16 hours of wet pulverization, preparing principal constituent thus is BaTiO
3, use the principal constituent of making so also to obtain same characteristic.In addition, use the principal constituent BaTiO that makes by hydro-thermal composite powder and oxalate method etc.
3, also obtained same characteristic.
These raw materials are mixed, make composition behind the sintering with respect to 100 moles of principal constituent BaTiO
3As shown in table 1, utilized the ball mill wet-mixed 16 hours, and after the drying, the preparation dielectric substance.
Then, with ball mill dielectric medium raw material 100 weight parts, acrylic resin 4.8 weight parts, vinyl acetic monomer 100 weight parts, mineral turpentine (ミ ネ ラ Le ス ピ リ Star ト) 6 weight parts, toluene 4 weight parts that obtain are mixed, obtain the dielectric layer thickener after becoming to stick with paste.
Then, after with three rollers the mixing one-tenth of Ni particle 100 weight parts, organic carrier (having dissolved ethyl cellulose 8 weight parts in diethylene glycol monobutyl ether 92 weight parts) 40 weight parts, diethylene glycol monobutyl ether 10 weight parts of median size 0.2～0.8 μ m being stuck with paste, obtain the interior electrode layer thickener.
Then, with Cu particle 100 weight parts, organic carrier (having dissolved ethyl cellulose 8 weight parts in diethylene glycol monobutyl ether 92 weight parts) 35 weight parts and diethylene glycol monobutyl ether 7 weight parts of median size 0.5 μ m are mixing become to stick with paste after, obtain the outer electrode thickener.
Then, use above-mentioned dielectric layer thickener, on the PET film, form the base substrate of thickness 4.5 μ m, on it the printing interior electrode layer with thickener after, peel off the base sheet from the PET film.Then, stacked these base sheets and protection have just obtained the base substrate with base sheet (not printing the base sheet of interior electrode layer with thickener) after pressure is sticking.The stacked number that makes the thin slice with internal electrode is 4 layers.
Then, the base substrate is cut into specified dimension, take off adhesive treatment, sintering and annealing, obtained the multilayer ceramic sintered compact.
The condition of taking off adhesive treatment is: in 15 ℃/hour of heat-up rates, 280 ℃ of temperature of maintenance, 8 hours hold-times, the air atmosphere.
Carrying out the agglomerating condition is: 200 ℃/hour of heat-up rates, keep temperature: the N behind 1280～1320 ℃, 2 hours hold-times, 300 ℃/hour of speed of cooling, humidification
2+ H
2(oxygen partial pressure 10 in the mixed-gas atmosphere
-9Atm.).
The annealed condition is: keep temperature: the N behind 900 ℃, temperature hold-time 9 hours, 300 ℃/hour of speed of cooling, humidification
2(oxygen partial pressure 10 in the gas atmosphere
-5Atm.).In addition, use the humidifier of 35 ℃ of water temperatures in the humidification of the atmosphere gas when sintering and annealing.
Transfer printing outer electrode thickener on end face, the N behind humidification then, have been ground after the end face of multilayer ceramic sintered compact by sandblast cleaning
2+ H
2In the atmosphere, sintering formed outer electrode after 10 minutes in 800 ℃, had obtained the multi-layer ceramic capacitor sample of structure shown in Figure 1.
The size of each sample that obtains like this is 3.2mm * 1.6mm * 0.6mm, and the quantity that is clipped in the dielectric layer in the interior electrode layer is 4, and its thickness is 3.5 μ m, and the thickness of interior electrode layer is 1.0 μ m.
The IR temperature dependency (giving up the throne) of the capacitor sample that evaluation obtains, temperature characteristics of capacitance (TC) and TC bias voltage.Result shown in the table 1.
The sample that mensuration obtains is at 150 ℃ insulation resistance IR
150Insulation resistance IR with 25 ℃
25, calculate giving up the throne shown in the following formula 1, estimate IR temperature dependency (giving up the throne).Metewand is serving as good more than-2.00.
Log (IR
150/ IR
25) ... formula 1
In addition, used variable temperatures IR tester in the mensuration of insulation resistance at each temperature, under the condition of measuring voltage 7.0V/ μ m, voltage application time 60s, measured.
The sample that obtains is measured electrostatic capacitance in-55 ℃～150 ℃ temperature range, estimated temperature characteristics of capacitance (T ℃).In the mensuration of electrostatic capacitance, use digital LCR meter (YHP makes 4274A), under the condition of frequency 1kHz, the horizontal 1Vrms of input signal, measure.Then, electrostatic capacitance change rate (Δ C/C, unit are %) under 150 ℃ the temperature environment that calculating temperature characteristics of capacitance in these temperature ranges becomes the poorest, check and whether to satisfy the X8R characteristic (55 ℃～150 ℃, Δ C/C=± 15% in), with the ◎ that is labeled as that satisfies, with ungratified being labeled as *.
Utilize digital LCR meter (YHP makes 4274A) under the bias voltage (volts DS) of 1kHz, 1Vrms, 7.0V/ μ m, make temperature change to 150 ℃ from-55 ℃, the sample that mensuration obtains, by 25 ℃ do not apply bias voltage the time measured value calculate the velocity of variation of electrostatic capacitance, estimate the TC bias voltage.In addition, in the mensuration of electrostatic capacitance, use digital LCR meter, under the condition of frequency 1kHz, the horizontal 1Vrms of input signal, measure.Metewand is serving as good more than-40%.
In addition, also the capacitor sample that obtains IR life-span, D.C. isolation strength at break, DC bias characteristic (volts DS of specific inductivity applies dependency) under specific inductivity (ε), dissipation loss (tan δ), the DC electric field have been estimated in the lump.
To capacitor sample, under 25 ℃ of reference temperatures, utilize digital LCR meter (YHP corporate system 4274A), under the condition of frequency 1kHz, input signal level (mensuration voltage) 1.0Vrms, measure electrostatic capacitance, calculate DIELECTRIC CONSTANT (no unit) by electrostatic capacitance.Its result, all sample has all obtained the good result more than 1000.
To capacitor sample, under 25 ℃ of reference temperatures, utilize digital LCR meter (YHP corporate system 4274A), under the condition of frequency 1kHz, input signal level (mensuration voltage) 1.0Vrms, measured dissipation loss (tan δ).Its result, all sample has all obtained the good result below 10%.
To capacitor sample, under the electric field of 200 ℃ of following 10V/ μ m, carry out accelerated test, insulation resistance is changed to time below the 1M Ω as life time, calculated the IR life-span under the DC electric field.Its result, all sample has all obtained the good result more than 10 hours.
To capacitor sample, apply volts DS by the speed of 100V/sec, the voltage (direct current disintegration voltage VB, current potential are V/ μ m) when measuring the leakage current that has detected 100mA calculates its mean value, obtains the D.C. isolation strength at break.Its result, all sample has all obtained the above good result of 100V/ μ m.
To capacitor sample, under certain temperature (25 ℃), measure gradually the variation (Δ C/C) that each sample is applied the electrostatic capacitance under the situation of volts DS, obtain the DC bias characteristic, the result who draws, confirmation applies high-voltage in whole samples after, electrostatic capacitance also is difficult to reduce, and has stable DC bias characteristic.
Table 1
| Sample number into spectrum | The 8th minor component | The rate of temperature change of electrostatic capacitance (%)+150 ℃ | The X8R characteristic | TC bias voltage (%) | The IR temperature dependency |
| The |
|||||
| 1* | 0 | -7.5 | ◎ | -38.0 | -2.45 |
| 2 | 0.5 | -8.6 | ◎ | -37.1 | -1.91 |
| 3 | 1 | -9.3 | ◎ | -36.1 | -1.86 |
| 4 | 1.5 | -9.8 | ◎ | -31.1 | -1.61 |
| 5 | 2 | -10.3 | ◎ | -27.3 | -1.51 |
| 6 | 2.5 | -11.5 | ◎ | -25.1 | -1.39 |
| 7 | 3 | -12.7 | ◎ | -23.5 | -1.35 |
| 8 | 3.5 | -13.8 | ◎ | -22.8 | -1.31 |
| 9* | 4 | -16.7 | × | -21.3 | -1.29 |
The sample of band " * " is represented comparative example.
Wherein, first minor component: MgCO
3=1.0 moles
Second minor component: (Ba
0.6, Ca
0.4) SiO
3=3.0 moles
The 3rd minor component: V
2O
5=0.1 mole
Fourth officer composition: Yb
2O
3=1.75 moles (converting by Yb is 3.5 moles)
The 5th minor component: CaZrO
3=1.5 moles
The 6th minor component: Y
2O
3=2.0 moles
The 7th minor component: MnCO
3=0.374 mole
The 8th minor component: Al
2O
3
Above-mentioned addition all is the addition with respect to 100 moles of principal constituents
As shown in table 1, if the content of the 8th minor component is very few, though then satisfy the X8R characteristic, giving up the throne of IR just surpasses-2.00, and the IR temperature dependency worsens, and the TC bias characteristic also worsens.If the content of the 8th minor component is too much,, can not satisfy the X8R characteristic though then improved the IR temperature dependency.
On the contrary, the content by making the 8th minor component is in proper range, and when satisfying the X8R characteristic, IR gives up the throne more than-2.00, can confirm to have improved the IR temperature dependency.
Except the kind that makes the 8th minor component raw material and content change shown in table 2～5, make capacitor sample similarly to Example 1, carried out same evaluation.
Table 2
| Sample number into spectrum | The 8th minor component | The rate of temperature change of electrostatic capacitance (%)+150 ℃ | The X8R characteristic | TC bias voltage (%) | The IR temperature dependency |
| The |
|||||
| 1* | 0 | -7.5 | ◎ | -38.0 | -2.45 |
| 11 | 0.5 | -7.9 | ◎ | -37.6 | -1.97 |
| 12 | 1 | -10.2 | ◎ | -36.7 | -1.91 |
| 13 | 1.5 | -11.4 | ◎ | -32.3 | -1.64 |
| 14 | 2 | -12.8 | ◎ | -28.1 | -1.59 |
| 15 | 2.5 | -13.7 | ◎ | -26.0 | -1.43 |
| 16 | 3 | -13.4 | ◎ | -24.2 | -1.38 |
| 17 | 3.5 | -14.5 | ◎ | -23.6 | -1.34 |
| 18* | 4 | -18.9 | × | -22.7 | -1.31 |
The sample of band " * " is represented comparative example.
Wherein, the composition of the composition of principal constituent, first～the 7th minor component is identical with table 1 with addition.
The 8th minor component: Cr
2O
3
Table 3
| Sample number into spectrum | The 8th minor component | The rate of temperature change of electrostatic capacitance (%)+150 ℃ | * 8R characteristic | TC bias voltage (%) | The IR temperature dependency |
| The |
|||||
| 1* | 0 | -7.5 | ◎ | -38.0 | -2.45 |
| 20 | 0.5 | -8.0 | ◎ | -37.5 | -1.95 |
| 21 | 1 | -9.6 | ◎ | -36.1 | -1.90 |
| 22 | 1.5 | -10.6 | ◎ | -32.1 | -1.70 |
| 23 | 2 | -11.2 | ◎ | -27.8 | -1.55 |
| 24 | 2.5 | -12.4 | ◎ | -25.4 | -1.40 |
| 25 | 3 | -13.4 | ◎ | -23.7 | -1.32 |
| 26 | 3.5 | -14.5 | ◎ | -23.1 | -1.36 |
| 27* | 4 | -17.9 | × | -22.1 | -1.31 |
The sample of band " * " is represented comparative example.
Wherein, the composition of the composition of principal constituent, first～the 7th minor component is identical with table 1 with addition.
The 8th minor component: Ge
2O
2
Table4
| Sample number into spectrum | The 8th minor component | The rate of temperature change of electrostatic capacitance (%)+150 ℃ | The X8R characteristic | TC bias voltage (%) | The IR temperature dependency |
| The | |||||
| 1* | 0 | -7.5 | ◎ | -38.0 | -2.45 |
| 29 | 0.5 | -8.2 | ◎ | -37.4 | -1.97 |
| 30 | 1 | -9.4 | ◎ | -35.9 | -1.92 |
| 31 | 1.5 | -10.4 | ◎ | -32.4 | -1.73 |
| 32 | 2 | -11.0 | ◎ | -28.1 | -1.58 |
| 33 | 2.5 | -12.2 | ◎ | -25.8 | -1.42 |
| 34 | 3 | -13.2 | ◎ | -23.8 | -1.34 |
| 35 | 3.5 | -14.4 | ◎ | -23.6 | -1.37 |
| 36* | 4 | -17.8 | × | -22.7 | -1.29 |
The sample of band " * " is represented comparative example.
Wherein, the composition of the composition of principal constituent, first～the 7th minor component is identical with table 1 with addition.
The 8th minor component: Ga
2O
3
Shown in table 2～table 4, even the 8th minor component raw material is become Cr
2O
3, Ge
2O
2, Ga
2O
3, also can confirm to have obtained Al with embodiment 1
2O
3Same effect.
Table 5
| Sample number into spectrum | The 8th minor component | The rate of temperature change of electrostatic capacitance (%)+150 ℃ | The X8R characteristic | TC bias voltage (%) | The IR temperature dependency | |
| Al 2O 3 | Cr 2O 3 | |||||
| Addition (mole) | ||||||
| 1* | 0 | 0 | -7.5 | ◎ | -38.0 | -2.45 |
| 38 | 1 | 0.25 | -8.1 | ◎ | -37.5 | -1.70 |
| 39 | 1 | 0.5 | -9.1 | ◎ | -36.5 | -1.49 |
| 40 | 1 | 0.75 | -10.5 | ◎ | -31.8 | -1.41 |
| 41 | 1 | 1 | -11.8 | ◎ | -27.8 | -1.39 |
| 42 | 1 | 1.5 | -12.8 | ◎ | -25.7 | -1.31 |
| 43 | 1 | 2 | -14.5 | ◎ | -24.1 | -1.30 |
| 44* | 1 | 3 | -15.9 | × | -23.1 | -1.29 |
| 45* | 1 | 3.5 | -17.5 | × | -22.6 | -1.28 |
The sample of band " * " is represented comparative example.
Wherein, the composition of the composition of principal constituent, first～the 7th minor component is identical with table 1 with addition.
The 8th minor component: Al
2O
3+ Cr
2O
3
As shown in table 5, even the 8th minor component raw material is become Al
2O
3And Cr
2O
3Complex form, also can confirm to have obtained and independent interpolation Al
2O
3The same effect of situation.
Comparative example 1
Except the kind that makes the 8th minor component raw material and content change as shown in table 6ly, make capacitor sample similarly to Example 1, carried out same evaluation.
Table 6
| Sample number into spectrum | The 8th minor component | The rate of temperature change of electrostatic capacitance (%)+150 ℃ | The X8R characteristic | TC bias voltage (%) | The IR temperature dependency | |
| P 2O 6 | K 2O | |||||
| Addition (mole) | ||||||
| 47* | 0.5 | - | -13.2 | ◎ | -40.1 | -2.61 |
| 48* | 1 | - | -14.1 | ◎ | -45.1 | -2.87 |
| 49* | 1.5 | - | -16.0 | × | -47.2 | -2.91 |
| 51* | - | 0.5 | -13.1 | ◎ | -40.7 | -2.86 |
| 52* | - | 1 | -16.9 | × | -46.8 | -3.00 |
The sample of band " * " is expressed comparative example.
Wherein, the composition of the composition of principal constituent, first～the 7th minor component is identical with table 1 with addition.
The 8th minor component: P
2O
5Or K
2O
As shown in table 6, the effective ionic radius when becoming 6 coordinations has broken away under the situation of cation element P (0.052nm), K (0.152nm) of proper range, can confirm, even content in proper range, can not obtain the effect that the 8th minor component adds.
Below, embodiment 3～6th, the embodiment that second viewpoint of the present invention relates to.
At first, as the starting raw material that is used to make dielectric substance, prepared the principal constituent raw material (BaTiO of median size 0.1～1 μ m respectively
3) and first～the 8th minor component raw material.Each raw material uses raw material similarly to Example 1.
Then, ready raw material is mixed, make composition behind the sintering with respect to 100 moles of principal constituent BaTiO
3Shown in table 7,8, utilized the ball mill wet-mixed 16 hours, make dielectric substance after making its drying, obtain the dielectric layer thickener similarly to Example 1.
Then, use the interior electrode layer thickener and the outer electrode thickener of above-mentioned dielectric layer thickener, making similarly to Example 1, obtained the sample of the multi-layer ceramic capacitor of structure shown in Figure 1 similarly to Example 1.
The size of each electrical condenser that obtains like this is 3.2mm * 1.6mm * 0.6mm, and the quantity that is clipped in the dielectric layer in the interior electrode layer is 4, and its thickness is 3.5～4.5 μ m, and the thickness of interior electrode layer is 1.0 μ m.
The capacitor sample that obtains IR temperature dependency (giving up the throne), high temperature accelerated aging, temperature characteristics of capacitance (TC) and TC bias voltage have been estimated.Result shown in the table 7,8.
Utilize method similarly to Example 1 to estimate IR temperature dependency (giving up the throne), temperature characteristics of capacitance (TC) and TC bias voltage.
The applying of volts DS that remains on 10V/ μ m in 200 ℃ by the sample that will obtain measured average life time under the state, estimated high temperature accelerated aging (HALT).In the present embodiment, will to begin to timing definition of giving up the throne of insulation resistance be the life-span from applying voltage.In addition, 10 capacitor samples have been carried out this high temperature accelerated aging.Metewand is decided to be more than 20 hours for good.
In addition, to the capacitor sample that obtains, utilization method has similarly to Example 1 been estimated IR life-span, D.C. isolation strength at break, the DC bias characteristic (volts DS of specific inductivity applies dependency) under specific inductivity (ε), dissipation loss (tan δ), the DC electric field in the lump, has obtained following result.
That is, relevant DIELECTRIC CONSTANT, all sample has obtained good result all more than 1000.
Relevant dissipation loss (tan δ), all sample has obtained good result all below 10%.
Relevant D.C. isolation strength at break, all sample all more than 100V/ μ m, has obtained good result.
Relevant DC bias characteristic even all sample all is to apply its electrostatic capacitance of high-voltage also to be not easy to reduce, has stable DC bias characteristic.
Table 7
| Sample number into spectrum | MgO | MnO | Mn/Mg | The rate of temperature change of electrostatic capacitance (%)+150 ℃ | The X8R characteristic | TC bias voltage (%) | The IR temperature dependency | HALT (h) |
| The addition mole | The addition mole | |||||||
| 101* | 0.3 | 0.05 | 0.17 | -8.7 | ◎ | -37.5 | -1.87 | 14 |
| 102 | 0.3 | 0.1 | 0.33 | -8.3 | ◎ | -37.6 | -1.84 | 22 |
| 103 | 0.3 | 0.15 | 0.50 | -8.4 | ◎ | -37.8 | -1.87 | 24 |
| 104* | 0.3 | 0.2 | 0.67 | -8.9 | ◎ | -37.9 | -1.86 | 12 |
| 105* | 0.5 | 0.1 | 0.20 | -8.6 | ◎ | -37.1 | -1.86 | 15 |
| 108 | 0.5 | 0.15 | 0.30 | -8.5 | ◎ | -37.3 | -1.85 | 24 |
| 107 | 0.5 | 0.2 | 0.40 | -8.5 | ◎ | -37.2 | -1.85 | 30 |
| 108* | 0.5 | 0.3 | 0.60 | -8.8 | ◎ | -37.1 | -1.86 | 16 |
| 109* | 0.75 | 0.2 | 0.27 | -8.8 | ◎ | -36.9 | -1.87 | 15 |
| 110 | 0.75 | 0.25 | 0.33 | -8.7 | ◎ | -36.7 | -1.87 | 22 |
| 111 | 0.75 | 0.3 | 0.40 | -8.6 | ◎ | -36.5 | -1.87 | 23 |
| 112* | 0.75 | 0.4 | 0.53 | -8.9 | ◎ | -36.2 | -1.88 | 13 |
The sample of band " * " is represented comparative example.
Wherein, the addition of MnO is the addition that converts by the Mn element,
Second minor component: (Ba
0.6, Ca
0.4) SiO
3=3.0 moles
The 3rd minor component: V
2O
5=0.1 mole
Fourth officer composition: Yb
2O
3=1.75 moles (converting by Yb is 3.5 moles)
The 5th minor component: CaZrO
3=1.5 moles
The 6th minor component: Y
2O
3=2.0 moles (converting by Y is 4.0 moles)
The 8th minor component: Al
2O
3=1.0 moles
Above-mentioned addition all is the addition with respect to 100 moles of principal constituents
Table 8
| Sample number into spectrum | MgO | MnO | Mn/Mg | The rate of temperature change of electrostatic capacitance (%)+150 ℃ | The X8R characteristic | TC bias voltage (%) | The IR temperature dependency | HALT (h) |
| The addition mole | The addition mole | |||||||
| 101* | 0.3 | 0.2 | 0.67 | -8.9 | ◎ | -37.5 | -1.86 | 12 |
| 106 | 0.5 | 0.2 | 0.40 | -8.5 | ◎ | -37.3 | -1.85 | 30 |
| 113 | 0.6 | 0.2 | 0.33 | -8.6 | ◎ | -37.6 | -1.86 | 31 |
| 114* | 0.8 | 0.2 | 0.25 | -8.7 | ◎ | -37.8 | -1.87 | 9.5 |
| 105* | 0.5 | 0.3 | 0.60 | -8.8 | ◎ | -37.2 | -1.86 | 16 |
| 115 | 0.6 | 0.3 | 0.50 | -8.7 | ◎ | -38.0 | -1.86 | 21 |
| 110 | 0.75 | 0.3 | 0.40 | -8.6 | ◎ | -37.9 | -1.87 | 23 |
| 116* | 0.8 | 0.3 | 0.38 | -8.6 | ◎ | -37.3 | -1.87 | 16 |
The sample of band " * " is represented comparative example.
Wherein, the addition of MnO is the addition that converts by the Mn element,
The composition of the composition of principal constituent, second～6th, eight minor components is identical with table 7 with addition.
In the table 7,8, first minor component and the 7th minor component are not the carbonate (MgCO that uses according to as raw material
3, MnCO
3), but (following in table 9～11 same) put down in writing according to the state of the oxide compound that contains in the dielectric layer behind the sintering (MgO, MnO).
Sample shown in the table 7 is that MgO is fixed as 0.3 mole, 0.5 mole, 0.75 mole respectively, by adjusting the addition of MnO, makes the sample of mol ratio (Mn/Mg) variation of Mn element and Mg element.In addition, the sample shown in the table 8 is that MnO is fixed as 0.2 mole, 0.3 mole respectively, by adjusting the addition of MgO, makes the sample of mol ratio (Mn/Mg) variation of Mn element and Mg element.In addition, in table 7 and table 8, for the identical sample number into spectrum of the sample mark of same composition.
As shown in table 7, in MgO is 0.3 mole sample 101～104, the mol ratio of Mn element and Mg element (Mn/Mg) all satisfies the X8R characteristic at the sample 102 and 103 of 0.3～0.5 scope, IR gives up the throne more than-2.00, improved the IR temperature dependency, and, can make high temperature accelerated aging (HALT) more than 20 hours, become good result.
On the other hand, respectively the mol ratio (Mn/Mg) of Mn element and Mg element is located at beyond the scope of the present invention i.e. 0.17,0.67 sample 101,104, its X8R characteristic and IR temperature dependency are all good, but high temperature accelerated aging (HALT) variation.
In addition, be that 0.5 mole of (sample 105～108), MgO are under the situation of 0.75 mole (sample 109～112) at MgO, in addition,, make in the situation (table 9) that MgO changes at fixing MnO, all become same result.But the sample of table 9 116 is because the content of MgO is too much, therefore thinks high temperature accelerated aging (HALT) variation.
The sample that the embodiment that shows that the present invention's second viewpoint relates to is shown respectively among Fig. 2 A, Fig. 3 A is the Mg element (Fig. 2 A) of sample 111 and the segregation status photo of Mn element (Fig. 3 A), and it is the Mg element (Fig. 2 B) of sample 112 and the segregation status photo of Mn element (Fig. 3 B) that the sample that shows comparative example is shown respectively among Fig. 2 B, Fig. 3 B.Can confirm according to these photos, in the sample of comparative example, have a lot of Mg elements and Mn elements segregation.On the contrary, in the sample of the embodiment that the present invention's second viewpoint relates to, can confirm to have suppressed these segregations.These photos are to analyze the photo that obtains by carrying out EPMA.
Except using Cr
2O
3Replace MnO as beyond the 7th minor component, similarly made capacitor sample, carried out same evaluation with the sample 109～112 of embodiment 3.
Table 9
| Sample number into spectrum | MgO | Cr 2O 3 | Cr/Mg | The rate of temperature change of electrostatic capacitance (%)+150 ℃ | The X8R characteristic | TC bias voltage (%) | The IR temperature dependency | HALT (h) |
| The addition mole | The addition mole | |||||||
| 117* | 0.75 | 0.2 | 0.27 | -8.6 | ◎ | -38.1 | -1.7 | 12 |
| 118 | 0.75 | 0.25 | 0.33 | -8.4 | ◎ | -38.3 | -1.69 | 22 |
| 119 | 0.75 | 0.3 | 0.40 | -8.2 | ◎ | -38.4 | -1.68 | 21 |
| 120* | 0.75 | 0.4 | 0.53 | -8.5 | ◎ | -38.5 | -1.68 | 11 |
The sample of band " * " is represented comparative example.
Wherein, Cr
2O
3Addition be the addition that converts by the Cr element,
The composition of the composition of principal constituent, second～6th, eight minor components is identical with table 7 with addition.
As shown in table 9, can confirm using Cr
2O
3Situation in also have and the same trend of situation of using MnO.
Embodiment 5
Except the content that makes MgO and MnO changes as shown in table 10ly, make capacitor sample similarly to Example 3, carry out same evaluation.
Table 10,
| Sample number into spectrum | MgO | MnO | Mn/Mg | The rate of temperature change of electrostatic capacitance (%)+150 ℃ | The X8R characteristic | TC bias voltage (%) | The IR temperature dependency | HALT (h) |
| The addition mole | The addition mole | |||||||
| 121* | 0 | 0.2 | - | -13.1 | ◎ | -42.1 | -1.9 | 5 |
| 122* | 0.5 | 0 | 0.00 | Because the dielectric layer semiconductor transformation is so can not measure | ||||
| 123* | 1.5 | 0.6 | 0.40 | -9.6 | ◎ | -35.2 | -1.96 | 10 |
The sample of band " * " is represented comparative example.
Wherein, the addition of MnO is the addition that converts by the Mn element,
The composition of the composition of principal constituent, second～the 6th minor component is identical with table 7 with addition.
As shown in table 10,121 result can confirm per sample, and under the situation of not adding MgO, high temperature accelerated aging (HALT) significantly reduces.In addition, 122 result can confirm per sample, under the situation of not adding MnO, and dielectric layer semiconductor transformation, the sample that does not obtain carrying out various evaluations.
In addition, 123 result can confirm per sample, under the too much situation of the content of MgO and MnO, for example, is that high temperature accelerated aging (HALT) also worsens under 0.4 the situation in the mol ratio (Mn/Mg) of Mn element and Mg element.
Embodiment 6
Except making the 8th minor component is Al
2O
3Content change as shown in table 11ly beyond, similarly make capacitor sample with the sample 107 of embodiment 3, carry out same evaluation.
Table 11
| Sample number into spectrum | MgO | MnO | Mn/Mg | Al 2O 3 | The rate of temperature change of electrostatic capacitance (%)+150 ℃ | The X8R characteristic | TC bias voltage (%) | The IR temperature dependency | HALT (h) |
| The addition mole | The addition mole | The addition mole | |||||||
| 124* | 0.5 | 0.2 | 0.40 | 0 | -8.2 | ◎ | -39.2 | -2.41 | 20 |
| 107 | 0.5 | 0.2 | 0.40 | 1 | -8.5 | ◎ | -37.2 | -1.85 | 30 |
| 125 | 0.5 | 0.2 | 0.40 | 2 | -10.9 | ◎ | -30.1 | -1.80 | 25 |
| 126 | 0.5 | 0.2 | 0.40 | 3 | -13.5 | ◎ | -25.2 | -1.51 | 20 |
| 127* | 0.5 | 0.2 | 0.40 | 4 | -15.3 | × | -24.0 | -1.37 | 15 |
The sample of band " * " is represented comparative example.
Wherein, the addition of MnO is the addition that converts by the Mn element,
The composition of the composition of principal constituent, second～the 6th minor component is identical with table 7 with addition.
As shown in table 11, can confirm, do not adding Al
2O
3Situation under, the IR temperature dependency worsens, in addition, at Al
2O
3The too much situation of addition under, temperature characteristics of capacitance worsens, and does not satisfy the X8R characteristic.
Claims (21)
1, a kind of dielectric ceramic composition, it contains:
The principal constituent that comprises barium titanate;
Comprise the first at least a minor component that is selected among MgO, CaO, BaO and the SrO;
Second minor component as sintering aid;
Comprise and be selected from V
2O
5, MoO
3And WO
3In the 3rd at least a minor component;
The fourth officer composition that comprises the oxide compound (wherein, R1 is selected from least a among Sc, Er, Tm, Yb and the Lu) of R1;
Comprise CaZrO
3Or CaO+ZrO
2The 5th minor component;
The 8th minor component that comprises the oxide compound (wherein, A is that the effective ionic radius when being selected from 6 coordinations is at least a in the cation element group of 0.065nm～0.085nm) of A,
With respect to 100 moles of above-mentioned principal constituents, the ratio of above-mentioned the 8th minor component is 0～4 mole (but do not comprise 0 mole and 4 moles, be the value that is converted into the A oxide compound).
2, dielectric ceramic composition as claimed in claim 1, the above-mentioned A of the oxide compound that comprises in wherein above-mentioned the 8th minor component are to be selected from least a in Al, Cr, Ga, the Ge cation element group.
3, dielectric ceramic composition as claimed in claim 1, wherein, with respect to 100 moles of above-mentioned principal constituents, the ratio of each minor component is:
First minor component: 0.1～3 mole,
Second minor component: 2～10 moles,
The 3rd minor component: 0.01～0.5 mole,
The fourth officer composition: 0.5～7 mole (wherein, the mole number of fourth officer composition is the independent ratio of R1),
The 5th minor component: 0＜the 5th minor component≤5 mole.
4, dielectric ceramic composition as claimed in claim 1, its oxide compound that further contains R2 (wherein, R2 is selected from least a among Y, Dy, Ho, Tb, Gd and the Eu) as the 6th minor component, with respect to 100 moles of the principal constituents that comprises barium titanate, the content of above-mentioned the 6th minor component is (wherein, the mole number of the 6th minor component is the independent ratio of R2) below 9 moles or 9 moles.
5, dielectric ceramic composition as claimed in claim 4, wherein, with respect to 100 moles of the principal constituents that comprises barium titanate, the total content of fourth officer composition and the 6th minor component is (wherein, the mole number of fourth officer composition and the 6th minor component is the independent ratio of R1 and R2) below 13 moles or 13 moles.
6, dielectric ceramic composition as claimed in claim 1, wherein above-mentioned second minor component is with being selected from SiO
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 at least a expression.
7, dielectric ceramic composition as claimed in claim 1, it further contains MnO as the 7th minor component, and with respect to 100 moles of the principal constituents that comprises barium titanate, the content of above-mentioned the 7th minor component is below 0.5 mole or 0.5 mole.
8, a kind of dielectric ceramic composition, it contains:
The principal constituent that comprises barium titanate;
First minor component that comprises MgO;
Second minor component as sintering aid;
Comprise and be selected from V
2O
5, MoO
3And WO
3In the 3rd at least a minor component;
The fourth officer composition that comprises the oxide compound (wherein, R1 is selected from least a among Sc, Er, Tm, Yb and the Lu) of R1;
Comprise CaZrO
3Or CaO+ZrO
2The 5th minor component;
Comprise MnO or Cr
2O
3The 7th minor component;
Comprise Al
2O
3The 8th minor component,
With respect to 100 moles of above-mentioned principal constituents, the ratio of above-mentioned first minor component, the 7th minor component, the 8th minor component is:
First minor component: 0.2～0.75 mole,
The 7th minor component: 0.1～0.3 mole (wherein, the mole number of the 7th minor component is the ratio that converts by Mn element or Cr element),
The 8th minor component: 0.5～4 mole (but not comprising 4 moles),
The Mn element that comprises in Mg element that comprises in above-mentioned first minor component and above-mentioned the 7th minor component, the mol ratio of Cr element have the relation of 0.3≤(Mn+Cr)/Mg≤0.5.
9, dielectric ceramic composition as claimed in claim 8, wherein, with respect to 100 moles of above-mentioned principal constituents, the ratio of above-mentioned second～the 5th minor component is:
Second minor component: 2～10 moles,
The 3rd minor component: 0.01～0.5 mole,
The fourth officer composition: 0.5～7 mole (wherein, the mole number of fourth officer composition is the independent ratio of R1),
The 5th minor component: 0＜the 5th minor component≤5 mole.
10, dielectric ceramic composition as claimed in claim 8, the oxide compound that wherein further contains R2 (wherein, R2 is selected from least a among Y, Dy, Ho, Tb, Gd and the Eu) as the 6th minor component, with respect to 100 moles of the principal constituents that comprises barium titanate, the content of above-mentioned the 6th minor component is (wherein, the mole number of the 6th minor component is the independent ratio of R2) below 9 moles or 9 moles.
11, dielectric ceramic composition as claimed in claim 10, wherein, with respect to 100 moles of the principal constituents that comprises barium titanate, the total content of fourth officer composition and the 6th minor component is (wherein, the mole number of fourth officer composition and the 6th minor component is the independent ratio of R1 and R2) below 13 moles or 13 moles.
12, dielectric ceramic composition as claimed in claim 8 is characterized in that, above-mentioned first minor component further comprises and is selected among CaO, BaO and the SrO one or more.
13, dielectric ceramic composition as claimed in claim 8, wherein, above-mentioned second minor component is with being selected from SiO
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 at least a expression.
14, a kind of electronic unit, it has the dielectric layer that is made of dielectric ceramic composition, and described dielectric ceramic composition contains:
The principal constituent that comprises barium titanate;
Comprise the first at least a minor component that is selected among MgO, CaO, BaO and the SrO;
Second minor component as sintering aid;
Comprise and be selected from V
2O
5, MoO
3And WO
3In the 3rd at least a minor component;
The fourth officer composition that comprises the oxide compound (wherein, R1 is selected from least a among Sc, Er, Tm, Yb and the Lu) of R1;
Comprise CaZrO
3Or CaO+ZrO
2The 5th minor component;
The 8th minor component that comprises the oxide compound (wherein, A is that the effective ionic radius when being selected from 6 coordinations is at least a in the cation element group of 0.065nm～0.085nm) of A,
With respect to 100 moles of above-mentioned principal constituents, the ratio of above-mentioned the 8th minor component is 0～4 mole (but do not comprise 0 mole and 4 moles, be the value that is converted into the A oxide compound).
15, a kind of multi-layer ceramic capacitor, this electrical condenser have dielectric layer and the alternately laminated capacitor element main body of interior electrode layer that is made of dielectric ceramic composition, and wherein said dielectric ceramic composition contains:
The principal constituent that comprises barium titanate;
Comprise the first at least a minor component that is selected among MgO, CaO, BaO and the SrO;
Second minor component as sintering aid;
Comprise and be selected from V
2O
5, MoO
3And WO
3In the 3rd at least a minor component;
The fourth officer composition that comprises the oxide compound (wherein, R1 is selected from least a among Sc, Er, Tm, Yb and the Lu) of R1;
Comprise CaZrO
3Or CaO+ZrO
2The 5th minor component;
The 8th minor component that comprises the oxide compound (wherein, A is selected from least a in the cation element group of Al, Cr, Ga, Ge) of A,
With respect to 100 moles of above-mentioned principal constituents, the ratio of above-mentioned the 8th minor component is 0～4 mole (but do not comprise 0 mole and 4 moles, be the value that is converted into the A oxide compound).
16, multi-layer ceramic capacitor as claimed in claim 15, wherein, in above-mentioned dielectric ceramic composition, each minor component with respect to the ratio of 100 moles of above-mentioned principal constituents is:
First minor component: 0.1～3 mole,
Second minor component: 2～10 moles,
The 3rd minor component: 0.01～0.5 mole,
The fourth officer composition: 0.5～7 mole (wherein, the mole number of fourth officer composition is the independent ratio of R1),
The 5th minor component: 0＜the 5th minor component≤5 mole.
17, multi-layer ceramic capacitor as claimed in claim 16, wherein, above-mentioned dielectric ceramic composition further contains the oxide compound (wherein, R2 is selected from least a among Y, Dy, Ho, Tb, Gd and the Eu) of R2 as the 6th minor component, contain MnO as the 7th minor component
With respect to 100 moles of the principal constituents that comprises barium titanate, the content of above-mentioned the 6th minor component is (wherein, the mole number of the 6th minor component is the independent ratio of R2) below 9 moles or 9 moles,
With respect to 100 moles of the principal constituents that comprises barium titanate, the content of above-mentioned the 7th minor component is below 0.5 mole or 0.5 mole.
18, a kind of electronic unit, it has the dielectric layer that is made of dielectric ceramic composition, and this dielectric ceramic composition contains:
The principal constituent that comprises barium titanate;
First minor component that comprises MgO;
Second minor component as sintering aid;
Comprise and be selected from V
2O
5, MoO
3And WO
3In the 3rd at least a minor component;
The fourth officer composition that comprises the oxide compound (wherein, R1 is selected from least a among Sc, Er, Tm, Yb and the Lu) of R1;
Comprise CaZrO
3Or CaO+ZrO
2The 5th minor component;
Comprise MnO or Cr
2O
3The 7th minor component;
The 8th minor component that comprises the oxide compound of Al,
With respect to 100 moles of above-mentioned principal constituents, the ratio of above-mentioned first minor component, the 7th minor component, the 8th minor component is:
First minor component: 0.2～0.75 mole,
The 7th minor component: 0.1～0.3 mole (but the mole number of the 7th minor component is the ratio that converts by Mn element or Cr element),
The 8th minor component: 0.5～4 mole (but not comprising 4 moles),
The Mn element that comprises in Mg element that comprises in above-mentioned first minor component and above-mentioned the 7th minor component, the mol ratio of Cr element have the relation of 0.3≤(Mn+Cr)/Mg≤0.5.
19, a kind of multi-layer ceramic capacitor, it has dielectric layer and the alternately laminated capacitor element main body of interior electrode layer that is made of dielectric ceramic composition, and wherein this dielectric ceramic composition contains:
The principal constituent that comprises barium titanate;
First minor component that comprises MgO;
Second minor component as sintering aid;
Comprise and be selected from V
2O
5, MoO
3And WO
3In the 3rd at least a minor component;
The fourth officer composition that comprises the oxide compound (wherein, R1 is selected from least a among Sc, Er, Tm, Yb and the Lu) of R1;
Comprise CaZrO
3Or CaO+ZrO
2The 5th minor component;
Comprise MnO or Cr
2O
3The 7th minor component;
The 8th minor component that comprises the oxide compound of Al,
With respect to 100 moles of above-mentioned principal constituents, the ratio of above-mentioned first minor component, the 7th minor component, the 8th minor component is,
First minor component: 0.2～0.75 mole,
The 7th minor component: 0.1～0.3 mole (mole number of the 7th minor component is the ratio that converts by Mn element or Cr element),
The 8th minor component: 0.5～4 mole (but not comprising 4 moles),
The Mn element that comprises in Mg element that comprises in above-mentioned first minor component and above-mentioned the 7th minor component, the mol ratio of Cr element have the relation of 0.3≤(Mn+Cr)/Mg≤0.5.
20, multi-layer ceramic capacitor as claimed in claim 19, wherein, in above-mentioned dielectric ceramic composition, with respect to 100 moles of above-mentioned principal constituents, the ratio of above-mentioned second～the 5th minor component is:
Second minor component: 2～10 moles,
The 3rd minor component: 0.01～0.5 mole,
The fourth officer composition: 0.5～7 mole (wherein, the mole number of fourth officer composition is the independent ratio of R1),
The 5th minor component: 0＜the 5th minor component≤5 mole.
21, multi-layer ceramic capacitor as claimed in claim 20, wherein, in above-mentioned dielectric ceramic composition, the oxide compound (wherein, R2 is selected from least a among Y, Dy, Ho, Tb, Gd and the Eu) that further contains R2 is as the 6th minor component,
With respect to 100 moles of the principal constituents that comprises barium titanate, the content of above-mentioned the 6th minor component is (wherein, the mole number of the 6th minor component is the independent ratio of R2) below 9 moles or 9 moles.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP250941/04 | 2004-08-30 | ||
| JP2004250941A JP4275036B2 (en) | 2004-08-30 | 2004-08-30 | Dielectric ceramic composition and electronic component |
| JP169895/05 | 2005-06-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1765824A true CN1765824A (en) | 2006-05-03 |
| CN100376507C CN100376507C (en) | 2008-03-26 |
Family
ID=36109733
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
|---|---|
| JP (1) | JP4275036B2 (en) |
| CN (1) | CN100376507C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434393C (en) * | 2005-04-04 | 2008-11-19 | Tdk株式会社 | Electronic device, dielectric ceramic composition, and method of production of the same |
| CN103102153A (en) * | 2011-11-11 | 2013-05-15 | 三星电机株式会社 | Dielectric composition and ceramic electronic component including the same |
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| JP4682559B2 (en) * | 2004-08-30 | 2011-05-11 | Ｔｄｋ株式会社 | Dielectric ceramic composition and electronic component |
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| JP2013173626A (en) * | 2012-02-23 | 2013-09-05 | Tdk Corp | Dielectric porcelain composition and ceramic electronic part |
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| EP0739019B1 (en) * | 1994-10-19 | 2003-12-03 | TDK Corporation | Multilayer ceramic chip capacitor |
| JP3348081B2 (en) * | 1999-10-19 | 2002-11-20 | ティーディーケイ株式会社 | Dielectric porcelain composition and electronic component |
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| CN1532166A (en) * | 2003-03-21 | 2004-09-29 | 广东风华高新科技集团有限公司 | Method for producing high dielectric constant ceramic powder and ceramic capacitor |
-
2004
- 2004-08-30 JP JP2004250941A patent/JP4275036B2/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| CN100376507C (en) | 2008-03-26 |
| JP2006062937A (en) | 2006-03-09 |
| JP4275036B2 (en) | 2009-06-10 |
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