JP4661203B2 - Ceramic electronic component and manufacturing method thereof - Google Patents

Description

  The present invention relates to a ceramic electronic component such as a multilayer ceramic capacitor and a manufacturing method thereof, and more particularly to a ceramic electronic component containing a dielectric layer having a high dielectric constant and a manufacturing method thereof.

  A multilayer ceramic capacitor, which is an example of an electronic component, includes, for example, a ceramic green sheet made of a predetermined dielectric ceramic composition raw material and an internal electrode layer of a predetermined pattern alternately stacked, and then a green chip obtained by integrating them, Manufactured by simultaneous firing. Since the internal electrode layer of the multilayer ceramic capacitor is integrated with the ceramic dielectric by firing, it is necessary to select a material that does not react with the ceramic dielectric. For this reason, as a material constituting the internal electrode layer, conventionally, an expensive noble metal such as platinum or palladium has been inevitably used.

  However, in recent years, dielectric ceramic compositions that can use inexpensive base metals such as nickel and copper have been developed, and a significant cost reduction has been realized.

  On the other hand, in recent years, there is a high demand for downsizing of electronic components due to higher density of electronic circuits, and downsizing and increasing capacity of multilayer ceramic capacitors are rapidly progressing. In order to cope with this reduction in size and increase in capacity, an attempt has been made to improve the dielectric constant of the dielectric ceramic composition constituting the dielectric layer of the multilayer ceramic capacitor.

  Conventionally, as a method of improving the dielectric constant, by previously baking the subcomponent raw material, adding to the main component raw material in a state of roasted powder, increasing the dispersibility of the subcomponent raw material, A method of increasing the dielectric constant by adding subcomponents as individual oxides and adjusting them to have a predetermined composition has been performed (see Patent Documents 1 to 3).

  However, in particular, when a method of improving the dielectric constant by changing the composition ratio of the subcomponents is employed, there is a problem that other characteristics are deteriorated while the dielectric constant is increased. Therefore, in order to cope with further downsizing and larger capacity, it is desired to improve the dielectric constant while maintaining desired characteristics.

Japanese Patent No. 2779882 Japanese Patent No. 3326513 Japanese Patent No. 2762427

  The present invention has been made in view of such a situation, and in a ceramic electronic component such as a multilayer ceramic capacitor, a ceramic electronic component including a dielectric layer having desired electrical characteristics and an improved dielectric constant, and It aims at providing the manufacturing method.

In order to achieve the above object, a ceramic electronic component according to the present invention comprises:
A ceramic electronic component containing a dielectric layer,
The dielectric layer comprises a main component comprising barium titanate;
A subcomponent containing Mg oxide and Si oxide,
A segregation phase mainly containing Mg and Si is formed in the dielectric layer.

  In the present invention, in the dielectric layer, at least a part of the Mg subcomponent and Si subcomponent is segregated to form a segregation phase mainly containing Mg and Si. In the present invention, by forming this segregation phase, it is possible to prevent the diffusion of Si into the grains, and to improve the dielectric constant without changing the blending ratio of other main components and subcomponents. Can do. Therefore, the dielectric constant can be improved while maintaining desired characteristics, particularly desired electrical characteristics (for example, IR temperature dependency, capacitance temperature characteristics, etc.).

  In the present invention, the segregation phase is compared with a main phase mainly composed of main components in which the oxide of Mg, the oxide of Si, and other additive subcomponents segregate in the dielectric layer. , Means a portion where these added subcomponents are present in high concentration. In particular, the segregation phase preferably has a Si content ratio of 10 or more times that of the main phase.

  In the present invention, when the ratio of the segregation phase in the cross-sectional area of the dielectric layer is 100% of the entire dielectric layer, the area ratio is preferably greater than 0% and less than 30%, more preferably Is 2% or more and 25% or less. When the ratio of the segregation phase is too large, the dielectric constant is deteriorated, and the IR (insulation resistance) temperature dependency tends to decrease.

  In the present invention, the maximum diameter of the segregation phase is preferably less than 3 μm, more preferably 0.1 to 2.5 μm. When the maximum diameter of the segregation phase is too large, IR temperature dependency tends to increase.

  The maximum particle size of the segregation phase means the particle size of the segregation phase having the maximum particle size in an arbitrary cross section of the dielectric layer. In the present invention, the particle size of the segregation phase means the longest linear distance among the linear distances from end to end of the segregation phase. That is, for example, when the cross-sectional shape of the segregation phase is circular, it means the length of its diameter, and when the cross-sectional shape of the segregation phase is elliptical, it means the length of its long side.

  In the present invention, the content of the Mg oxide in the dielectric layer is 0.5 to 11 mol, more preferably 0.8 to 10 mol in terms of MgO with respect to 100 mol of the main component. . If the content of Mg oxide is too small, the segregation phase is difficult to form, and it tends to be difficult to improve the dielectric constant. On the other hand, when the content is too large, the IR temperature dependency tends to increase.

In the present invention, the content of the Si oxide in the dielectric layer is 0.01 to 2.0 mol, more preferably 0.5 to _{2 in} terms of SiO _{2 with} respect to 100 mol of the main component. 0.0 mole. When the content of Si oxide is too small, sintering tends to be difficult. On the other hand, when the content is too large, the ratio of the segregation phase in the cross-sectional area of the dielectric layer becomes too high, the dielectric constant decreases, and the IR temperature dependency tends to increase.

  Preferably, the ratio of Ba and Ti in the barium titanate is 0.998 ≦ Ba / Ti ≦ 1.020. If the ratio of Ba to Ti (Ba / Ti) is too small, grains will grow too much during firing, and the temperature characteristics of the capacitance will decrease, resulting in EIA standard X6S characteristics (−55 to 105 ° C., ΔC). = ± 22% or less). On the other hand, if the ratio of Ba and Ti is too large, sintering tends to be difficult.

In the present invention, preferably, the dielectric layer includes, as a subcomponent, an oxide of Mn, an oxide of Ba, an oxide of Ca, an oxide of Ti, and an oxide of R (where R is Sc, Y , La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu),
The content of each oxide with respect to 100 moles of the main component is calculated in terms of MnO, BaO, CaO, TiO ₂ and R ₂ O ₃ , respectively.
Mn oxide: 0.1 to 0.5 mol,
Ba oxide: 0.01 to 2 mol,
Ca oxide: 0.01-2 mol,
Ti oxide: 0.5 to 11 mol,
R oxide: 0.01-3.0 mol,
And
More preferably,
Mn oxide: 0.1 to 0.3 mol,
Ba oxide: 0.01-1.0 mol,
Ca oxide: 0.01 to 1.0 mol,
Ti oxide: 0.8 to 10 mol,
R oxide: 0.01-2.5 mol,
It is.

  In the present invention, the oxide of R is preferably an oxide of Y, an oxide of Tb, an oxide of Dy, or an oxide of Yb, and among these, an oxide of Y is particularly preferable.

The method for producing a ceramic electronic component of the present invention includes
A method for producing any one of the above ceramic electronic components,
Examples subcomponent materials will form the dielectric layer, characterized by the use of MgTiO ₃ powder.

In the production method of the present invention, MgTiO ₃ powder, which is a composite oxide of Mg and Ti, is used as a raw material for the subcomponent. In the present invention, since MgTiO ₃ powder is used in this way, Si can be segregated together with Mg in the fired dielectric layer, and the diffusion of Si into the grains can be effectively prevented. Therefore, according to the manufacturing method of the present invention, a segregation phase mainly containing Mg and Si can be effectively formed.

In the production method of the present invention, MgTiO ₃ powder having an average particle diameter of preferably 0.3 μm or less, more preferably 0.01 to 0.2 μm is used as the MgTiO ₃ powder. If the average particle diameter of the MgTiO ₃ powder used as the subcomponent raw material is too large, the ratio of the segregation phase in the cross-sectional area of the dielectric layer becomes too high, the dielectric constant decreases, and the IR temperature dependency is also high. It tends to grow. The average particle diameter of the MgTiO ₃ powder can be determined by measuring a volume-based cumulative 50% diameter (D50 diameter) by a method using light scattering such as laser diffraction.

  The ceramic electronic component of the present invention and the ceramic electronic component obtained by the manufacturing method of the present invention are not particularly limited, but include multilayer ceramic capacitors, piezoelectric elements, chip inductors, chip varistors, chip thermistors, chip resistors, and other surface mounts. (SMD) chip type electronic components are exemplified.

  According to the present invention, in a ceramic electronic component such as a multilayer ceramic capacitor, a segregation phase mainly containing Mg and Si is formed as a dielectric layer contained in these electronic components. The dielectric constant can be improved while maintaining the characteristics (for example, IR temperature dependence, capacitance temperature characteristics, etc.).

In addition, according to the production method of the present invention, MgTiO ₃ powder, which is a composite oxide of Mg and Ti, is used as a raw material for subcomponents. Therefore, the segregation phase mainly containing Mg and Si is effectively reduced. Can be formed.

Hereinafter, the present invention will be described based on embodiments shown in the drawings.
FIG. 1 is a cross-sectional view of a multilayer ceramic capacitor according to an embodiment of the present invention.
FIG. 2A is a photograph showing the segregation state of Mg expressed by EPMA analysis of the microstructure of the dielectric layer according to the embodiment of the present invention, and FIG. 2B is the dielectric according to the embodiment of the present invention. A photograph showing the segregation state of Si expressed by EPMA analysis of the microstructure of the layer, FIG. 2 (C) is a diagram for explaining a method for measuring the maximum diameter of the segregation phase,
FIG. 3 is a FESEM (field emission scanning electron microscope) photograph of a dielectric layer according to an embodiment of the present invention.

Multilayer ceramic capacitor 1
As shown in FIG. 1, a multilayer ceramic capacitor 1 according to an embodiment of the present invention includes a capacitor element body 10 having a configuration in which dielectric layers 2 and internal electrode layers 3 are alternately stacked. At both ends of the capacitor element body 10, a pair of external electrodes 4 are formed which are electrically connected to the internal electrode layers 3 arranged alternately in the element body 10. The shape of the capacitor element body 10 is not particularly limited, but is usually a rectangular parallelepiped shape. Moreover, there is no restriction | limiting in particular also in the dimension, What is necessary is just to set it as a suitable dimension according to a use.

  The internal electrode layers 3 are laminated so that the end faces are alternately exposed on the surfaces of the two opposite ends of the capacitor element body 10. The pair of external electrodes 4 are formed at both ends of the capacitor element body 10 and are connected to the exposed end surfaces of the alternately arranged internal electrode layers 3 to constitute a capacitor circuit.

Dielectric layer 2
The dielectric layer 2 contains a dielectric ceramic composition.
In the present embodiment, the dielectric ceramic composition includes a main component containing barium titanate, and Mg oxide and Si oxide as subcomponents. Furthermore, the segregation phase mainly containing Mg and Si is formed in the dielectric layer 2 of the present embodiment.

  The barium titanate contained as the main component preferably has a ratio of Ba and Ti of 0.998 ≦ Ba / Ti ≦ 1.020. If the ratio of Ba and Ti (Ba / Ti) is too small, grains will grow too much during firing, and the temperature characteristics of the capacitance will decrease, resulting in EIA standard X6S characteristics (−55 to 105 ° C., ΔC = within ± 22%). On the other hand, if the ratio of Ba and Ti is too large, sintering tends to be difficult.

  The content of the Mg oxide is 0.5 to 11 mol, more preferably 0.8 to 10 mol in terms of MgO with respect to 100 mol of the main component. If the content of Mg oxide is too small, a segregation phase, which will be described later, becomes difficult to form, and it tends to be difficult to improve the dielectric constant. On the other hand, when the content is too large, the IR temperature dependency tends to increase.

The content of the Si oxide is 0.01 to 2.0 mol, more preferably 0.5 to 2.0 mol in terms of SiO _{2 with} respect to 100 mol of the main component. When the content of Si oxide is too small, sintering tends to be difficult. On the other hand, when the content is too large, the ratio of the segregation phase in the cross-sectional area of the dielectric layer becomes too high, the dielectric constant deteriorates, and the IR temperature dependency tends to increase.

  In the dielectric layer 2 of the present embodiment, a segregation phase mainly including Mg and Si is formed. The segregation phase 2 is formed by segregation of at least part of the Mg subcomponent and the Si subcomponent described above.

  In the present embodiment, by forming a segregation phase having Mg and Si in the dielectric layer 2, diffusion of Si into the grains can be prevented. Therefore, the dielectric constant can be improved without changing the mixing ratio of other main components and subcomponents, and the dielectric constant can be improved while maintaining desired characteristics, particularly desired electrical characteristics. it can. In addition, it is preferable that the segregation phase of this embodiment has a Si content ratio of 10 times or more as compared with a main phase mainly composed of main components.

  The content ratio of the segregation phase in the dielectric layer 2 is preferably greater than 0% and less than 30% when the entire dielectric layer 2 is 100% in the area ratio in the cross-sectional area of the dielectric layer 2. More preferably, it is 2% or more and 25% or less. When the ratio of the segregation phase is too large, the dielectric constant decreases and the IR temperature dependency tends to increase.

  The maximum diameter of the segregation phase is preferably less than 3 μm, more preferably 0.1 to 2.5 μm. When the maximum diameter of the segregation phase is too large, IR temperature dependency tends to increase.

  In the segregation phase 2, Mg and Si are contained as respective oxides or composite oxides. Further, the segregation phase 2 may contain elements other than Mg and Si, such as Ti.

  In the present embodiment, in addition to the Mg and Si oxides described above, an oxide of Mn, an oxide of Ba, an oxide of Ca, an oxide of Ti, and an oxide of R (wherein R is Sc, Y, It is preferable to further contain at least one selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu).

The contents of Mn oxide, Ba oxide, Ca oxide, Ti oxide, and R oxide are respectively MnO, BaO, CaO, TiO ₂ and R _{2 with} respect to 100 mol of the main component. O ₃ conversion
Mn oxide: 0.1 to 0.5 mol,
Ba oxide: 0.01 to 2 mol,
Ca oxide: 0.01-2 mol,
Ti oxide: 0.5 to 11 mol,
R oxide: 0.01-3.0 mol,
It is preferable that
More preferably,
Mn oxide: 0.1 to 0.3 mol,
Ba oxide: 0.01-1.0 mol,
Ca oxide: 0.01 to 1.0 mol,
Ti oxide: 0.8 to 10 mol,
R oxide: 0.01-2.5 mol,
It is.

  The oxide of Mn has the effect of promoting sintering, the effect of increasing IR (insulation resistance), and the effect of improving the high temperature load life. If the content of the Mn oxide is too small, the above-described effects cannot be obtained, and the temperature characteristics of the capacitance are lowered, and the X6S characteristics of the EIA standard tend not to be satisfied. When the amount is too large, the relative permittivity tends to decrease.

  The oxide of Ba and the oxide of Ca have the effect of improving the sinterability of the dielectric layer 2. If the content of Ba oxide and Ca oxide is too small, sintering tends to be difficult, and if too much, the dielectric constant tends to decrease.

The Ba oxide and Ca oxide, together with the above-described Si oxide, are added in the form of a composite oxide represented by (Ba, Ca) _x SiO _{2 + x} , so that the sinterability is particularly improved. Can be improved.

The oxide of Ti is contained in the dielectric ceramic composition constituting the dielectric layer 2 as MgTiO ₃ powder as will be described later. In this embodiment, the above-described Mg oxide is a composite oxide with Ti. By adding as a certain MgTiO ₃ , the above-mentioned segregation phase can be effectively formed.

  The oxide of R exhibits the effect of improving the high temperature load life. If the content of the oxide of R is too small, such an effect is insufficient and the capacity-temperature characteristics are deteriorated. On the other hand, if the content is too large, the sinterability tends to deteriorate. Among the oxides of R, a Y oxide, a Tb oxide, a Dy oxide, and a Yb oxide are preferable, and a Y oxide is particularly preferable.

  The thickness of the dielectric layer 2 is not particularly limited, but is preferably 4.5 μm or less per layer, more preferably 3.5 μm or less, and even more preferably 3.0 μm or less. Although the minimum of thickness is not specifically limited, For example, it is about 0.5 micrometer.

Internal electrode layer 3
The conductive material contained in the internal electrode layer 3 is not particularly limited, but a relatively inexpensive base metal can be used because the constituent material of the dielectric layer 2 has reduction resistance. As the base metal used as the conductive material, Ni or Ni alloy is preferable. The Ni alloy is preferably an alloy of Ni and one or more elements selected from Mn, Cr, Co and Al, and the Ni content in the alloy is preferably 95% by weight or more. In addition, in Ni or Ni alloy, various trace components, such as P, may be contained about 0.1 wt% or less. Moreover, you may form the internal electrode layer 3 using a commercially available electrode. What is necessary is just to determine the thickness of the internal electrode layer 3 suitably according to a use etc.

External electrode 4
The conductive material contained in the external electrode 4 is not particularly limited, but in the present invention, inexpensive Ni, Cu, and alloys thereof can be used. What is necessary is just to determine the thickness of the external electrode 4 suitably according to a use etc.

Manufacturing Method of Multilayer Ceramic Capacitor 1 The multilayer ceramic capacitor of the present embodiment is the same as the conventional multilayer ceramic capacitor, in which a green chip is produced by a normal printing method or sheet method using a paste, fired, and then externally It is manufactured by printing or transferring an electrode and firing. Hereinafter, the manufacturing method will be specifically described.

  First, a dielectric ceramic composition powder contained in a dielectric layer paste is prepared, and this is made into a paint to prepare a dielectric layer paste.

  The dielectric layer paste may be an organic paint obtained by kneading a dielectric ceramic composition powder and an organic vehicle, or may be a water-based paint.

  As the dielectric ceramic composition powder, the main component and subcomponent oxides and mixtures thereof, and composite oxides can be used. In addition, various compounds that become the above oxides and composite oxides by firing, For example, carbonates, oxalates, nitrates, hydroxides, organometallic compounds, and the like can be appropriately selected and used in combination. What is necessary is just to determine content of each compound in a dielectric ceramic composition powder so that it may become a composition of the above-mentioned dielectric ceramic composition after baking. The particle size of the dielectric ceramic composition powder is usually about 0.1 to 1 [mu] m in average before the coating.

In the present embodiment, MgTiO ₃ powder, which is a composite oxide of Mg and Ti, is used as a raw material for the Mg oxide and Ti oxide contained in the dielectric layer 2. By using MgTiO ₃ powder as a raw material for these oxides, a segregation phase mainly containing Mg and Si can be effectively formed in the dielectric layer 2 after firing. In this embodiment, Si can be effectively segregated by using the Mg oxide and Ti oxide raw materials in the form of MgTiO ₃ , and as a result, mainly contains Mg and Si. It is thought that a segregation phase is formed.

The MgTiO ₃ powder is obtained by, for example, mixing an Mg raw material such as MgCO ₃ and a Ti raw material such as TiO ₂ in a water system using a ball mill or the like, then calcining, and pulverizing the obtained calcined product. Can be prepared. In the present embodiment, as the MgTiO ₃ powder, a powder having an average particle diameter of preferably 0.3 μm or less, more preferably 0.01 to 0.2 μm is used. If the average particle size of the MgTiO ₃ powder is too large, the ratio of the segregation phase in the cross-sectional area of the dielectric layer 2 becomes too high, the dielectric constant decreases, and the IR temperature dependency tends to increase. .

In the present embodiment, the method for preparing the dielectric ceramic composition powder composed of the main component raw material powder, MgTiO ₃ powder and other subcomponent raw material powder is not particularly limited. and the raw material powder, and other subcomponent materials powders other than MgTiO ₃ powder, and a method of calcining was added and mixed MgTiO ₃ powder calcined obtained, the main component raw material powder, and MgTiO ₃ powder, Examples include a method of mixing other subcomponent raw material powders at once.

Specifically, for example, other subcomponent raw material powders other than MgTiO ₃ powder are pre-baked to make a roasted powder, and the roasted powder and the main component raw material powder are calcined in advance, and then MgTiO ₃ powder Or a method of mixing the roasted powder, the main component raw material powder, and the MgTiO ₃ powder at once. In addition, as another method, other subcomponent raw material powders other than MgTiO ₃ powder are pre-coated on the surface of the main component raw material powder, and then MgTiO ₃ powder is added and mixed, or subcomponents An example is a method in which at least a part of the raw material is doped into the main component raw material, and then the MgTiO ₃ powder and the remaining subcomponent raw material powder are added and mixed.

  An organic vehicle is obtained by dissolving a binder in an organic solvent. The binder used for the organic vehicle is not particularly limited, and may be appropriately selected from usual various binders such as ethyl cellulose and polyvinyl butyral. Further, the organic solvent to be used is not particularly limited, and may be appropriately selected from various organic solvents such as terpineol, butyl carbitol, acetone, toluene, and the like, depending on a method to be used such as a printing method or a sheet method.

  Further, when the dielectric layer paste is used as a water-based paint, a water-based vehicle in which a water-soluble binder or a dispersant is dissolved in water and a dielectric material may be kneaded. The water-soluble binder used for the water-based vehicle is not particularly limited, and for example, polyvinyl alcohol, cellulose, water-soluble acrylic resin, or the like may be used.

  The internal electrode layer paste is obtained by kneading the above-mentioned organic vehicle with various conductive metals and alloys as described above, or various oxides, organometallic compounds, resinates, etc. that become the above-mentioned conductive materials after firing. Prepare.

  The external electrode paste may be prepared in the same manner as the internal electrode layer paste described above.

  The internal electrode layer paste and the external electrode paste may be commercially available electrode pastes, or may be pastes of commercially available electrode materials.

  There is no restriction | limiting in particular in content of the organic vehicle in each above-mentioned paste, For example, what is necessary is just about 1-5 weight% of binders, for example, about 10-50 weight% of binders. Each paste may contain additives selected from various dispersants, plasticizers, dielectrics, insulators, and the like as necessary. The total content of these is preferably 10% by weight or less.

  When the printing method is used, the dielectric layer paste and the internal electrode layer paste are printed and laminated on a substrate such as PET, cut into a predetermined shape, and then peeled from the substrate to obtain a green chip.

  When the sheet method is used, a dielectric layer paste is used to form a green sheet, the internal electrode layer paste is printed thereon, and these are stacked to form a green chip.

  Before firing, the green chip is subjected to binder removal processing. As binder removal conditions, the temperature rising rate is preferably 5 to 300 ° C./hour, the holding temperature is preferably 180 to 400 ° C., and the temperature holding time is preferably 0.5 to 24 hours. The firing atmosphere is air or a reducing atmosphere.

The atmosphere at the time of green chip firing may be appropriately determined according to the type of conductive material in the internal electrode layer paste, but when a base metal such as Ni or Ni alloy is used as the conductive material, the oxygen content in the firing atmosphere The pressure is preferably 10 ⁻⁷ to 10 ⁻³ Pa. When the oxygen partial pressure is less than the above range, the conductive material of the internal electrode layer may be abnormally sintered and may be interrupted. Further, when the oxygen partial pressure exceeds the above range, the internal electrode layer tends to be oxidized.

  Moreover, the holding temperature at the time of baking becomes like this. Preferably it is 1100-1400 degreeC, More preferably, it is 1200-1300 degreeC. If the holding temperature is less than the above range, the densification is insufficient. Reduction of the body porcelain composition is likely to occur.

As other firing conditions, the rate of temperature rise is preferably 50 to 500 ° C./hour, more preferably 200 to 300 ° C./hour, and the temperature holding time is preferably 0.5 to 8 hours, more preferably 1 to 3 hours. The time and cooling rate are preferably 50 to 500 ° C./hour, more preferably 200 to 300 ° C./hour. Further, the firing atmosphere is preferably a reducing atmosphere, and as the atmosphere gas, for example, a mixed gas of N ₂ and H ₂ can be used by humidification.

  When firing in a reducing atmosphere, it is preferable to anneal the capacitor element body. Annealing is a process for re-oxidizing the dielectric layer, and this can significantly increase the IR lifetime, thereby improving the reliability.

The oxygen partial pressure in the annealing atmosphere is preferably 10 ^{−1 to} 10 Pa. When the oxygen partial pressure is less than the above range, it is difficult to reoxidize the dielectric layer, and when it exceeds the above range, the internal electrode layer tends to be oxidized.

  The holding temperature at the time of annealing is preferably 1100 ° C. or less, particularly 500 to 1100 ° C. When the holding temperature is lower than the above range, the dielectric layer is not sufficiently oxidized, so that the IR is low and the high temperature load life is likely to be shortened. On the other hand, when the holding temperature exceeds the above range, not only the internal electrode layer is oxidized and the capacity is lowered, but the internal electrode layer reacts with the dielectric substrate, the capacity temperature characteristic is deteriorated, the IR is lowered, and the high temperature is increased. The load life is likely to decrease. Note that annealing may be composed of only a temperature raising process and a temperature lowering process. That is, the temperature holding time may be zero. In this case, the holding temperature is synonymous with the maximum temperature.

As other annealing conditions, the temperature holding time is preferably 0 to 20 hours, more preferably 2 to 10 hours, and the cooling rate is preferably 50 to 500 ° C./hour, more preferably 100 to 300 ° C./hour. . Further, as the annealing atmosphere gas, for example, humidified N ₂ gas or the like is preferably used.

In the above-described binder removal processing, firing and annealing, for example, a wetter or the like may be used to wet the N ₂ gas or mixed gas. In this case, the water temperature is preferably about 5 to 75 ° C.
The binder removal treatment, firing and annealing may be performed continuously or independently.

The capacitor element main body obtained as described above is subjected to end face polishing, for example, by barrel polishing or sand blasting, and the external electrode paste is applied and fired to form the external electrode 4. The firing conditions of the external electrode paste are preferably, for example, about 10 minutes to 1 hour at 600 to 800 ° C. in a humidified mixed gas of N ₂ and H ₂ . Then, if necessary, a coating layer is formed on the surface of the external electrode 4 by plating or the like.
The multilayer ceramic capacitor of the present invention thus manufactured is mounted on a printed circuit board by soldering or the like and used for various electronic devices.

  In the present embodiment, a segregation phase mainly including Mg and Si is formed on the dielectric layer 2. Therefore, the diffusion of Si into the grains can be prevented, and the dielectric constant of the dielectric layer 2 can be improved without changing the blending ratio of other main components and subcomponents. Therefore, in the multilayer ceramic capacitor 1, it is possible to improve the dielectric constant while maintaining desired characteristics, particularly desired electrical characteristics.

Furthermore, in the manufacturing method of the present embodiment, MgTiO ₃ powder, which is a composite oxide of Mg and Ti, is used as a raw material for Mg oxide and Ti oxide. Therefore, a segregation phase mainly containing Mg and Si can be effectively formed.

  As mentioned above, although embodiment of this invention has been described, this invention is not limited to the embodiment mentioned above at all, and can be variously modified within the range which does not deviate from the summary of this invention.

  For example, in the above-described embodiment, the multilayer ceramic capacitor is exemplified as the ceramic electronic component according to the present invention. However, the ceramic electronic component according to the present invention is not limited to the multilayer ceramic capacitor, and has a dielectric layer having the above configuration. Anything can be used.

  Hereinafter, although this invention is demonstrated based on a more detailed Example, this invention is not limited to these Examples.

Example 1
First, as a starting material for preparing a dielectric ceramic composition constituting the dielectric layer, a main component raw material powder (BaTiO ₃ , Ba / Ti = 1.005) having an average particle size of 0.2 μm and each of the sub-materials shown below Ingredient raw materials were prepared.
MnO: 0.1 mol Y ₂ O ₃ : 0.2 mol BaO: 0.6 mol CaO: 0.2 mol SiO ₂ : 0.8 mol MgO: 1.0 mol The amount of each subcomponent added is mainly It is the number of moles relative to 100 moles of BaTiO _{3 as a} component.

Next, the raw material powders of these main components and subcomponents and MgTiO ₃ powder were wet-mixed for 16 hours by a ball mill and dried to obtain a dielectric ceramic composition powder. The MgTiO ₃ powder was obtained by weighing MgCO ₃ powder and TiO ₂ powder, mixing with a ball mill using water as a solvent, and then calcining under conditions of 1300 ° C. and 3 hours. The calcined product was again prepared by pulverizing with a ball mill using water as a solvent to 0.3 μm or less. In this example, the addition amount of MgTiO ₃ powder was changed as shown in Table 1, and samples Nos. 1 to 7 having different addition amounts of MgTiO ₃ powder were prepared.

  Next, 100 parts by weight of the obtained dielectric ceramic composition powder after drying, 10 parts by weight of polyvinyl butyral resin, 5 parts by weight of dibutyl phthalate (DOP) as a plasticizer, and 100 parts by weight of alcohol as a solvent. The paste was mixed by a ball mill to obtain a dielectric layer paste.

  In this example, a capacitor electrode paste (a paste mainly containing Ni particles as conductive particles) was used as the internal electrode layer paste.

  Using these pastes, the multilayer ceramic chip capacitor 1 shown in FIG. 1 was manufactured as follows.

  First, using the obtained dielectric layer paste, a green sheet was formed on a PET film by a doctor blade method so that the thickness after drying was 4 μm. Next, an electrode pattern having a thickness of 1.5 μm was printed on the green sheet by screen printing using the internal electrode layer paste, thereby producing a green sheet on which the electrode pattern was printed. Next, separately from the above green sheet, a green sheet with no electrode pattern printed on the PET film was manufactured by a doctor blade method using the dielectric layer paste.

And each green sheet manufactured above was laminated | stacked in the following order, and the green chip | tip was manufactured by pressing the obtained laminated body.
That is, first, green sheets on which no electrode patterns were printed were laminated until the total thickness reached 300 μm. On top of that, five green sheets printed with electrode patterns were laminated. Further thereon, a green sheet on which no electrode pattern was printed was laminated until the total thickness reached 300 μm to obtain a laminate. The obtained laminate was heated and pressurized under the conditions of a temperature of 80 ° C. and a pressure of 1 t / cm ² to obtain a green chip.

Next, the obtained green chip was cut into a predetermined size and subjected to binder removal processing, firing and annealing under the following conditions to obtain a multilayer ceramic fired body.
The binder removal treatment conditions were temperature rising rate: 30 ° C./hour, holding temperature: 250 ° C., temperature holding time: 8 hours, and atmosphere: in the air.
Firing conditions are: temperature rising rate: 200 ° C./hour, holding temperature: 1240 ° C., temperature holding time: 2 hours, cooling rate: 300 ° C./hour, atmospheric gas: humidified N ₂ and 0.5 to 5% by volume. A mixed gas with H ₂ (oxygen partial pressure: 10 ⁻⁷ Pa) was used.
The annealing conditions were as follows: temperature rising rate: 200 ° C./hour, holding temperature: 1050 ° C., temperature holding time: 2 hours, cooling rate: 300 ° C./hour, atmospheric gas: humidified N ₂ gas (oxygen partial pressure: 10 ⁻¹ Pa).
Note that a wetter with a water temperature of 5 to 75 ° C. was used for humidifying the atmospheric gas during firing and annealing.

  Next, after polishing the end face of the obtained multilayer ceramic fired body by sand blasting, In-Ga was applied as an external electrode to obtain samples 1 to 7 of the multilayer ceramic capacitor shown in FIG. The size of the obtained capacitor sample was 3.2 mm × 1.6 mm × 1.0 mm, and the number of dielectric layers sandwiched between internal electrode layers was four.

  For each of the obtained capacitor samples, the area ratio of the segregated phase mainly containing Mg and Si, the maximum diameter of the segregated phase, the dielectric constant, the IR temperature dependency, and the temperature characteristics of the capacitance were measured by the following methods. .

Area ratio of segregation phase, maximum diameter of segregation phase First, the obtained capacitor sample was cut along a plane perpendicular to the internal electrode, and the cut surface was polished. Next, EPMA analysis was performed on the polished surface, and the area ratio and maximum diameter of the segregated phase mainly containing Mg and Si were measured from the results of element mapping of the Mg element and the Si element. The results are shown in Table 1. The EPMA analysis was performed on the dielectric layer portion of the polished surface, and the observation field of view was 30 × 30 μm. In observation, a region was selected in which the internal electrode portion did not enter the observation field.

  2A shows an element mapping photograph of the Mg element of Sample No. 12 in Example 3, and FIG. 2B shows an element mapping photograph of the Si element of the same portion. FIG. 2C is a diagram for explaining a method for measuring the maximum diameter of the segregation phase. That is, in this example, first, as shown in FIG. 2 (C), the length of the longest straight line among the linear distances from the end of the segregation phase is defined as the segregation phase particle size. The particle size of the phase was measured. As a result of the measurement, the maximum particle size of the segregated phases obtained was determined as the maximum diameter of the segregated phase.

The capacitor sample obtained by FESEM (field emission scanning electron microscope) measurement was cut in a plane perpendicular to the internal electrode in the same manner as described above, and the cut surface was polished. And about this grinding | polishing surface, the dielectric material layer was measured by FESEM (field emission type scanning electron microscope). A photograph obtained as a result of the measurement is shown in FIG. FIG. 3 is a photograph of sample number 6. From FIG. 3, the size of the segregation phase can be confirmed.

Dielectric constant ε
First, at a reference temperature of 25 ° C., a capacitor with a frequency of 1 kHz and an input signal level (measurement voltage) of 1.0 Vrms is input with a digital LCR meter (YHP 4284A), and the capacitance C is measured. did. The dielectric constant ε (no unit) was calculated based on the thickness of the dielectric layer, the effective electrode area, and the capacitance C obtained as a result of the measurement. A larger dielectric constant ε is preferable. The results are shown in Table 1.

IR Temperature Dependence First, with respect to the capacitor sample, an insulation resistance IR _{25 at} 25 ° C. and an insulation resistance IR ₁₈₀ at 180 ° C. were measured. The insulation resistance was measured by using an insulation resistance meter (R8340A manufactured by Advantest) at 25 ° C. and 180 ° C., and measuring the insulation resistance IR (unit: Ω) after applying DC 7 V / μm for 60 seconds. Subsequently, the ratio (IR ₁₈₀ / IR ₂₅ ) between the insulation resistance values IR ₁₈₀ and IR ₂₅ was calculated. In this example, a sample having IR ₁₈₀ / IR ₂₅ of ¼ or more was considered good. The results are shown in Table 1. In Table 1, samples with IR ₁₈₀ / IR ₂₅ of ¼ or more were designated as “◯”, and samples with less than ¼ were designated as “x”.

Capacitance Temperature Characteristics Capacitor samples were measured for capacitance at −55 ° C., 25 ° C., and 105 ° C., and changes in capacitance at −55 ° C. and 105 ° C. with respect to capacitance at 25 ° C. The rate ΔC (unit:%) was calculated. The rate of change in capacitance is preferably close to 0% (small absolute value). In this example, a sample in which the rate of change in electrostatic capacitance satisfies the X6S characteristic of the EIA standard (−55 to 105 ° C., ΔC = within ± 22%) is considered good. The results are shown in Table 1. In Table 1, samples that satisfy the X6S characteristics are indicated by “◯”, and samples that do not satisfy the X6S characteristics are indicated by “X”.

Evaluation 1
Table 1 shows the added amount of subcomponents of Samples 1 to 7, the area ratio of the segregation phase, the maximum diameter of the segregation phase, the dielectric constant, the IR temperature dependency, and the capacitance temperature characteristics.
As shown in Table 1, Samples 2 to 6 of Examples in which the addition amount of MgTiO ₃ is more than 0 mole and less than or equal to 10 moles with respect to 100 moles of the main component are segregated phases mainly containing Mg and Si. And the area ratio of the segregation phase and the maximum diameter of the segregation phase are within the preferred range of the present invention, the dielectric constant is high, the IR temperature dependency, and the temperature characteristics of the capacitance are also good. became. In particular, as shown in FIGS. 2A and 2B which are photographs of Mg segregation and Si segregation of sample number 12 of Example 3, Mg segregation (FIG. 2A) and Si The segregation (FIG. (B)) occurred in almost the same place, and the same tendency was confirmed in each sample of Example 1. That is, it can be confirmed that a segregation phase mainly containing Mg and Si is formed.

On the other hand, in the sample 1 of the comparative example in which MgTiO ₃ was not added as a raw material of the subcomponent, a segregation phase having Mg and Si was not formed, and the dielectric constant was higher than that of the samples 2 to 6 of the examples. The result was lower.

In addition, sample 7 of the reference example in which the addition amount of MgTiO ₃ was 11 mol had a maximum segregation phase diameter of 3 μm and a dielectric constant as high as 4000, but it was inferior in IR temperature dependency. I have.

From these results, in order to improve the dielectric constant while maintaining other electrical characteristics (for example, IR temperature dependence, capacitance temperature characteristics), a segregation phase mainly including Mg and Si is formed. It was desirable that, preferably, the maximum diameter of the segregation phase was confirmed to be less than 3 μm. Furthermore, from the above results, it can be confirmed that a segregation phase mainly containing Mg and Si can be effectively formed by adding in the form of MgTiO ₃ powder as a subcomponent raw material. It was confirmed that the amount of ₃ powder added was preferably 10 mol or less with respect to 100 mol of the main component.

Example 2
In Example 1, capacitor samples 8 and 9 were obtained in the same manner as in Example 1 except that MgO powder and TiO ₂ powder were used instead of MgTiO ₃ powder. The area ratio, the maximum diameter of the segregation phase, the dielectric constant, the IR temperature dependency, and the temperature characteristics of the capacitance were measured.

As shown in Table 2, in sample 8, MgO powder: 1 mol, TiO ₂ powder: 1 mol, and in sample 9, MgO powder: 2 mol, TiO ₂ powder: 1 mol. In Sample 9, the composition ratio of the dielectric layer after firing was made substantially the same as that of Sample 3 in Example 1.

Evaluation 2
Table 2 shows the added amounts of subcomponents of Samples 8 and 9, the area ratio of the segregation phase, the maximum diameter of the segregation phase, the dielectric constant, the IR temperature dependency, and the temperature characteristics of the capacitance.
As shown in Table 2, in Comparative Examples 8 and 9 using MgO powder and TiO ₂ powder instead of MgTiO ₃ powder, neither segregation phase containing Mg and Si was formed, and the dielectric constant was As a result, the IR temperature dependency was poor. In particular, the sample 9 of the comparative example was inferior in the dielectric constant and IR temperature dependency although the composition ratio was substantially the same as the sample 3 of the example 1.

Example 3
Except for the addition amount of the subcomponent raw material powders shown in Table 3, the capacitor samples 10 to 14 were obtained in the same manner as in Example 1, and the area ratio of the segregation phase and segregation in the same manner as in Example 1. The maximum diameter of the phase, dielectric constant, IR temperature dependency and capacitance temperature characteristics were measured. In particular, in each sample (samples 10 to 14) of Example 3, MgO powder was not used as a raw material for the accessory component.

Evaluation 3
Table 3 shows the additive amount of the subcomponents of Samples 10 to 14, the area ratio of the segregation phase, the maximum diameter of the segregation phase, the dielectric constant, the IR temperature dependency, and the temperature characteristics of the capacitance.
As shown in Table 3, all the samples 10 to 13 of the examples in which the addition amount of the subcomponent raw material powder was changed had a segregation phase mainly containing Mg and Si, and the area of the segregation phase. The ratio and the maximum diameter of the segregation phase were within the preferred range of the present invention, the dielectric constant was high, the IR temperature dependency, and the temperature characteristics of the capacitance were good. From this result, it was confirmed that the effects of the present invention were achieved even when the addition amount of the subcomponent raw material powder was changed.

In addition, in the sample 14 of the reference example in which the addition amount of SiO ₂ is outside the preferable range of the present invention, the area ratio of the segregation phase is 30%, the maximum diameter of the segregation phase is 3 μm, and the dielectric constant and IR temperature dependence The result was inferior.

Example 4
In Example 1, in place of the MgTiO ₃ powder, that was used CaTiO ₃ powder or SrTiO ₃ powder, and except for changing the addition amount of the other subcomponent materials, the capacitor in the same manner as in Example 1 Sample 15 To 17 and the area ratio of the segregation phase, the maximum diameter of the segregation phase, the dielectric constant, the IR temperature dependency, and the temperature characteristics of the capacitance were measured in the same manner as in Example 1. The amount of CaTiO ₃ or SrTiO ₃ added was the amount shown in Table 4, respectively.

Evaluation 4
Table 4 shows the addition amount of the subcomponents of Samples 15 to 17, the area ratio of the segregation phase, the maximum diameter of the segregation phase, the dielectric constant, the IR temperature dependency, and the temperature characteristics of the capacitance.
As shown in Table 4, in place of the MgTiO ₃ powder, samples 15 to 17 of the comparative example using CaTiO ₃ powder, SrTiO ₃ powder having the same crystal structure as MgTiO ₃ are both having Mg and Si A segregation phase was not formed, resulting in a low dielectric constant.

FIG. 1 is a cross-sectional view of a multilayer ceramic capacitor according to an embodiment of the present invention. 2A is a photograph showing the segregation state of Si expressed by EPMA analysis of the microstructure of the dielectric layer according to the embodiment of the present invention, and FIG. 2B is the dielectric according to the embodiment of the present invention. A photograph showing the segregation state of Mg expressed by EPMA analysis of the fine structure of the layer, FIG. 2C is a diagram for explaining a method for measuring the maximum particle size of the segregation phase. FIG. 3 is a FESEM (field emission scanning electron microscope) photograph of a dielectric layer according to an embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Multilayer ceramic capacitor 10 ... Capacitor element main body 2 ... Dielectric layer 3 ... Internal electrode layer 4 ... External electrode 200 ... Segregation phase

Claims (8)

A ceramic electronic component containing a dielectric layer,
The dielectric layer comprises a main component comprising barium titanate;
A subcomponent containing Mg oxide and Si oxide,
As the subcomponent, Mn oxide, Ba oxide, Ca oxide, Ti oxide and R oxide (wherein R is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, And at least one selected from Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu),
The content of each oxide with respect to 100 moles of the main component is calculated in terms of MnO, BaO, CaO, TiO ₂ and R ₂ O ₃ , respectively.
Mn oxide: 0.1 to 0.5 mol,
Ba oxide: 0.01 to 2 mol,
Ca oxide: 0.01-2 mol,
Ti oxide: 0.5 to 11 mol,
R oxide: 0.01-3.0 mol,
And
A ceramic electronic component, wherein a segregation phase mainly containing Mg and Si is formed in the dielectric layer.   2. The ceramic electron according to claim 1, wherein a ratio of the segregation phase in a cross-sectional area of the dielectric layer is an area ratio of greater than 0% and less than 30% when the entire dielectric layer is 100%. parts.   The ceramic electronic component according to claim 1 or 2, wherein a maximum diameter of the segregation phase is less than 3 µm. The content of the Mg oxide in the dielectric layer is 0.5 to 11 mol in terms of MgO with respect to 100 mol of the main component,
4. The ceramic electronic component according to claim 1, wherein the content of the Si oxide is 0.01 to 2.0 mol in terms of SiO _{2 with} respect to 100 mol of the main component.   The ceramic electronic component according to claim 1, wherein a ratio of Ba and Ti in the barium titanate is 0.998 ≦ Ba / Ti ≦ 1.020. The oxide of R is, the ceramic electronic component according to claim 1 which is an oxide of Y. A method of manufacturing a ceramic electronic component according to any one of claims 1 to 6
A method for manufacturing a ceramic electronic component, wherein MgTiO ₃ powder is used as a raw material of a subcomponent that forms the dielectric layer. Examples MgTiO ₃ powder, a manufacturing method of a ceramic electronic component according to claim 7 having an average particle size using the MgTiO ₃ powder is 0.3μm or less.

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