JP4720193B2 - Dielectric ceramic and manufacturing method thereof, and multilayer ceramic capacitor - Google Patents

Description

  The present invention relates to a dielectric ceramic, a method of manufacturing the same, and a multilayer ceramic capacitor. More specifically, the electric field induced strain (hereinafter referred to as “electrostriction”) generated when a voltage is applied is small, and a squeal generated by the electrostriction is generated. The present invention relates to a small dielectric ceramic and a manufacturing method thereof.

Among ABO ₃ perovskite dielectric ceramics suitable for multilayer ceramic capacitors, it is known that the main phase particles constituting the dielectric ceramic have a so-called “core-shell structure”. This "core shell" means that it consists of two regions of "shell" where the concentration of the additive component such as rare earth is high and "core" where the concentration of the additive component such as rare earth is low, and the "shell" region is Compared with the “core” region, the higher the concentration of the additive component, the lower the Curie temperature, that is, the lower the ferroelectricity. This “core-shell structure” can be obtained, for example, by adding an additive component containing a rare earth element or the like to a main component such as barium titanate and firing under appropriate conditions.

A method for manufacturing a dielectric ceramic having the “core-shell structure” as described above is disclosed in Patent Document 1. That is, the starting material is an ABO ₃ compound (A is Ba, Ba and Ca, or Ba, Ca and Sr, and B is Ti, or Ti and Zr), and the average powder diameter is A main component powder having a thickness of 0.1 to 0.3 μm is prepared, and each of the rare earth element compound containing at least one rare earth element having an atomic number of 57 to 71, an Mg compound, an Mn compound, a BaZrO _3, and an Si compound. Preparing a sub-component powder, mixing the main component powder and the sub-component powder to obtain a mixed powder, forming the mixed powder to obtain a compact, and reducing the compact A ceramic crystal contained in the non-reducing dielectric ceramic obtained by the firing step has a core-shell structure and a core diameter <0.4. A non-reducing dielectric ceramic that satisfies the grain diameter condition, has an average grain diameter of 0.15 to 0.8 μm, and is not less than 1.5 times the average powder diameter of the main component powder. It is a manufacturing method.

According to the method of manufacturing a non-reducing dielectric ceramic disclosed in Patent Document 1, a dielectric ceramic having a flat temperature characteristic of dielectric constant and high reliability under a high electric field can be obtained. Therefore, it is possible to realize a monolithic ceramic capacitor that is small and has a large capacity, and that has a small noise due to electrostriction.
JP 2004-345927 A

  However, the dielectric ceramic disclosed in Patent Document 1 has a problem that the electrostriction when an electric field of 30 kV / mm is applied is still inadequate, 0.074 to 0.082%. If the electrostriction of the multilayer ceramic capacitor is large, there is a problem that it causes a large squeal.

  Accordingly, an object of the present invention is to provide a dielectric ceramic that has a small electrostriction generated when an electric field is applied, preferably has a large dielectric constant ε, and has a flat temperature characteristic of the dielectric constant.

  Another object of the present invention is to provide a method for producing a dielectric ceramic that satisfies the above required characteristics.

  Furthermore, another object of the present invention is to provide a multilayer ceramic capacitor using the above-mentioned dielectric ceramic, having a small size and a large capacity, good temperature characteristics, and small noise due to electrostriction.

  In order to solve the technical problem described above, the dielectric ceramic according to the present invention is characterized by having the following configuration.

That is, the present invention includes the _{(Ba 1-xy Ca x Sr} y) (Ti 1-z Zr z) O 3 ( however, 0 ≦ x + y ≦ 0.15,0 ≦ z ≦ 0.3), and the _{(Ba 1-xy Ca x Sr} y) (Ti 1-z Zr z) O 3 100 parts by mol relative to the rare earth element R (Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, 4 to 30 mol parts of at least one of Ho, Er, Tm, Yb, and Lu) and 2 to 30 mol parts of BaZrO ₃ (however, the total value with 100z does not exceed 30). in the body the ceramic, the dielectric ceramic main phase grains, the _{(Ba 1-xy Ca x Sr} y) (Ti 1-z Zr z) O 3 and the be the solid solution consisting of a perovskite structure containing a rare earth element R , The main phase particles are in two regions, that is, a first concentration of the rare earth element is high. And the second region having a low concentration of the rare earth element, and the average concentration of the rare earth element in the first region is three times the molar ratio of the average concentration of the rare earth element in the second region. In addition, when the cross section of the dielectric ceramic is observed, the D90 value in the diameter distribution of the second region is less than 0.25 μm.

  Further, when the arbitrary cross section is observed, it is desirable that the D50 value in the diameter distribution of the second region is 0.05 μm or more.

Furthermore, it is also preferable to contain 1 to 20 mol parts of Mg and 1 to 15 mol parts or more of Si with respect to 100 mol parts of the ABO ₃ .

The dielectric ceramic of the present invention is manufactured, for example, by a manufacturing method including the following steps.
_{That, (Ba 1-xy Ca x} Sr y) (Ti 1-z Zr z) O 3 ( however, 0 ≦ x + y ≦ 0.15,0 ≦ z ≦ 0.3) first raw material composed mainly of Preparing a powder, a second raw material powder containing BaZrO ₃ as a main component, and a third raw material powder containing at least a rare earth compound, and mixing the first raw material powder and the second raw material powder in a liquid; A dielectric ceramic comprising a step of dispersing, then adding, mixing and drying a third raw material powder in the liquid to obtain a fourth raw material powder, and forming and firing the fourth raw material powder The average particle size of the second raw material powder is 1/30 to 1/3 of the average particle size of the first raw material powder.

  The present invention is also directed to a multilayer ceramic capacitor.

  That is, in the multilayer ceramic capacitor comprising a plurality of laminated dielectric ceramic layers, an internal electrode disposed between the dielectric ceramic layers, and an external electrode electrically connected to the internal electrode, the dielectric ceramic The multilayer ceramic capacitor is characterized in that the layer is formed of the dielectric ceramic of the present invention.

  As described above, according to the dielectric ceramic of the present invention, since there is almost no coarse second region in the main phase particles, electrostriction during application of a medium-high voltage electric field is reduced. In addition, since the average diameter of the second region is relatively large, and further, by setting the ceramic composition in an appropriate range, ε is as high as 500 or more, and the dielectric constant temperature characteristic becomes flat.

  Therefore, the multilayer ceramic capacitor using the dielectric ceramic of the present invention is small in size and large capacity, has a capacitance temperature characteristic satisfying the X7S characteristic, and has a small squeal due to electrostriction.

  First, a multilayer ceramic capacitor, which is the main use of the dielectric ceramic of the present invention, will be described. FIG. 1 is a cross-sectional view showing a general multilayer ceramic capacitor 1.

  The multilayer ceramic capacitor 1 includes a rectangular parallelepiped ceramic multilayer body 2. The ceramic laminate 2 includes a plurality of laminated dielectric ceramic layers 3 and a plurality of internal electrodes 4 and 5 formed along a specific interface between the plurality of dielectric ceramic layers 3. The internal electrodes 4 and 5 are formed so as to reach the outer surface of the ceramic laminate 2, but are drawn to the internal electrode 4 and the other end surface 7 that are drawn to one end face 6 of the ceramic laminate 2. The internal electrodes 5 are alternately arranged inside the ceramic laminate 2 so that electrostatic capacity can be obtained via the dielectric ceramic layer 3.

  The conductive material of the internal electrodes 4 and 5 is preferably nickel or a nickel alloy, copper or a copper alloy, or silver or a silver alloy, which is low cost.

  In order to take out the above-described capacitance, on the outer surface of the ceramic laminate 2 and on the end faces 6 and 7, so as to be electrically connected to any one of the internal electrodes 4 and 5, External electrodes 8 and 9 are respectively formed. As the conductive material contained in the external electrodes 8 and 9, the same conductive material as in the case of the internal electrodes 4 and 5 can be used, and silver, palladium, a silver-palladium alloy, and the like can also be used. The external electrodes 8 and 9 are formed by applying and baking a conductive paste obtained by adding glass frit to such metal powder.

  Further, first plating layers 10 and 11 made of nickel, copper or the like are formed on the external electrodes 8 and 9 as required, and a second plating layer made of solder, tin or the like is further formed thereon. Plating layers 12 and 13 are formed, respectively.

Next, details of the dielectric ceramic of the present invention will be described. The dielectric ceramic of the present invention is a solid solution composed of a perovskite structure represented by ABO ₃ (A includes Ba and B includes Ti) and includes a rare earth element R, and the main phase particles include: A dielectric ceramic composed of two regions, ie, a first region having a high concentration of the rare earth element and a second region having a low concentration of the rare earth element, and an arbitrary cross section of the dielectric ceramic was observed. The D90 value in the diameter distribution of the second region is less than 0.25 μm. A schematic view of this cross section is shown in FIG.

When the rare earth element R is dissolved in the main phase particle 11, it is divided into a first region 12 where the concentration of the rare earth element is high and a second region 13 where the concentration of the rare earth element is low. At this time, for example, when ABO ₃ is a BaTiO ₃ system, since the first region is more solid-dissolved in the rare earth than the second region, the Curie temperature is lowered and the ferroelectricity is lowered.

  As described above, when the ferroelectricity is lowered, the electrostriction is reduced. This is because the electrostriction, that is, the electric field induced strain here includes not only the original “electrostriction” proportional to the square of the electric field but also distortion caused by the ferroelectricity proportional to the first power of the electric field. Because. That is, in order to reduce electrostriction, the area (actually volume) of the second region 13 may be reduced.

  However, the most important factor for electrostriction reduction is not that the average value of the diameter of the second region 13 is small, but that there should be no coarse second region 13 even if it is a small number. That is, when taking a cumulative distribution curve of the diameters of a large number of second regions 13, it is required that the D90 value is small, not the D50 value. Specifically, in the dielectric ceramic of the present invention, the D90 value in the diameter of the second region 13 is less than 0.25 μm regardless of the diameter of the main phase particles 11. As shown in the schematic cross-sectional view of FIG. 3, even if the D50 value is small, if the D90 value is large, the electrostriction increases to 0.055% or more, and the problem of squeal increases. Therefore, the present invention is essentially different from the prior art that focuses on the average value of the area ratio of the second region to the main phase particles.

  Suppose two cases where the total volume of the second region is substantially the same, that is, a case where there are a small number of large second regions and a case where there are a large number of small second regions. In this case, in the latter case, the ferroelectricity is weakened by the size effect of the ferroelectric material, and the electrostriction is reduced. Furthermore, since the latter case has a larger surface area as a boundary with the first region having a smaller electrostriction than the former case, the distortion due to the ferroelectric domain inversion in the second region is less. It is constrained and the electrostriction is considered to be further reduced. For this reason, even when the volume ratio between the first region and the second region is fixed in the entire dielectric ceramic, the dielectric ceramic having a large number of small second regions as in the present invention can reduce electrostriction. It is effective.

  Therefore, the first region 12 and the second region 13 in the main phase particle 11 may each be composed of a plurality of regions.

  In the dielectric ceramic of the present invention, the average concentration of the rare earth element in the first region 12 is preferably 3 times or more in terms of molar ratio with respect to the average concentration of the rare earth element in the second region 13. If it is less than 3 times, the difference in characteristics between the first region 12 and the second region 13 becomes small, and a dielectric ceramic satisfying desired dielectric constant and temperature characteristics cannot be obtained.

  Further, the D50 value in the diameter distribution of the second region 13 is preferably 0.05 μm or more. If it is less than 0.05 μm, the ferroelectricity of the dielectric ceramic as a whole will be low, and the dielectric constant will be low, below 500. Also, the temperature characteristic of the capacitance cannot satisfy the X7S characteristic.

Here, an embodiment of a specific composition of the dielectric ceramic of the present invention will be described. That is, ABO ₃ is _{(Ba 1-xy Ca x Sr} y) (Ti 1-z Zr z) O 3 ( however, 0 ≦ x + y ≦ 0.15,0 ≦ z ≦ 0.3), the ABO ₃ 4 to 30 mol parts of rare earth element R (at least one of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) with respect to 100 mol parts , BaZrO ₃ is a dielectric ceramic containing 2 to 30 mole parts (however, the total value with 100z does not exceed 30).

The main component of the main phase particles 11 is preferably a BaTiO ₃ system, where Ba may be replaced with Sr or Ca, and Ti may be substituted with a predetermined amount of Zr. In addition to adjusting the characteristics, the rare earth element R has an effect of forming a first region 12 and a second region 13 by dissolving in the main phase particle 11. Zr is also a factor affecting the dielectric constant and temperature characteristics, but it is preferable to add an appropriate amount separately as BaZrO ₃ .

Furthermore, it is preferable to contain 1 to 20 mol parts of Mg and 1 to 15 mol parts or more of Si with respect to 100 mol parts of the ABO ₃ .

  When the above composition is satisfied, the dielectric constant is as high as 500 or more, and the temperature characteristic is good, that is, the change rate from −55 ° C. to 125 ° C. based on the capacitance at 25 ° C. is ± 22% or less. A dielectric ceramic satisfying the above is obtained. In the above composition range, the temperature at which the change rate of the dielectric constant becomes maximum within the above temperature range is 125 ° C., and thus the change rate at 125 ° C. is used as an index of temperature characteristics.

  Note that Zr as an element may be partially substituted with Hf. Hf has almost the same action as Zr, and even if a part thereof is substituted, the object of the present invention is not affected.

  When the Sr substitution amount exceeds 0.15, the dielectric constant becomes less than 500, which is not preferable. On the other hand, when the Ca substitution amount exceeds 0.15, the temperature characteristics deteriorate, which is not preferable. Further, when the Sr substitution and the Ca substitution are performed at the same time, if the total substitution amount exceeds 0.15, the dielectric constant is lowered and the temperature characteristics are deteriorated, which is not preferable.

When the content of the rare earth element R with respect to 100 parts by mole of (Ba _1-xy Ca _x Sr _y ) (Ti _{1 -z} Zr _z ) O ₃ is less than 4 parts by mole, the temperature characteristics are deteriorated, which is not preferable. When it exceeds 30 mol parts, the dielectric constant becomes low, which is not preferable.

BaZrO ₃ is preferably contained in an amount of 2 mol parts or more and 30 mol parts or less with respect to 100 mol parts of (Ba _1-xy Ca _{x S r y} ) (Ti _1-z Zr _z ) O ₃ . However, when it exceeds 30 mol parts in total with the substitution amount of Zr 100z, the dielectric constant is lowered and the temperature characteristics are deteriorated. On the other hand, when the amount is less than 2 mole parts, the temperature characteristics deteriorate, which is not preferable.

If the content for the _{(Ba 1-xy Ca x Sr} y) (Ti 1-z Zr z) O 3 100 molar parts of Mg is less than 1 part by mol, the temperature characteristic is deteriorated, which is undesirable. On the other hand, when it exceeds 20 parts by mole, the dielectric constant is lowered and the temperature characteristics are deteriorated, which is not preferable.

By containing 1 mol part or more of Si with respect to 100 mol parts of (Ba _1-xy Ca _{x S r y} ) (Ti _1-z Zr _z ) O ₃ , the sinterability of the dielectric ceramic is improved. However, if the content exceeds 15 mol parts, the dielectric constant is lowered.

Next, an embodiment of a method for producing a dielectric ceramic according to the present invention will be described. That is, the dielectric ceramic manufacturing method of the present invention includes a first raw material powder mainly containing ABO ₃ (A containing Ba and B containing Ti), and a second raw material powder mainly containing BaZrO _3. And a step of preparing a third raw material powder containing at least a rare earth compound, and mixing and dispersing the first raw material powder and the second raw material powder in a liquid, and then the third raw material in the liquid A method for producing a dielectric ceramic, comprising: adding a powder, mixing and drying to obtain a fourth raw material powder; and forming and firing the fourth raw material powder, wherein the second raw material The average particle size of the powder is 1/30 to 1/3 of the average particle size of the first raw material powder.

As a result, the fourth raw material powder is in a state where the fine second raw material powder is sufficiently dispersed around the first raw material powder. As an example, FIG. 4 shows a schematic diagram of a state in which fine BaZrO ₃ powder particles 32 are dispersed in BaTiO ₃ powder particles 31. In FIG. 4, the description of the third raw material powder is omitted. Although it is preferable that the third raw material powder is sufficiently dispersed, the level of dispersion required is not as high as that of the second raw material powder.

When the fourth raw material powder in which the fine BaZrO ₃ powder particles 32 are sufficiently dispersed in this way is molded and fired, the diameter distribution of the second region 13 of the sintered dielectric ceramic becomes sharp, Generation of a coarse second region can be prevented. Therefore, the D50 value and D90 value in the diameter distribution of the second region 13 can be easily controlled to a desired value by a method such as controlling the firing temperature. Further, when the firing temperature is increased, solid solution of the rare earth element R in the main phase particles 11 is promoted, and the second region tends to be reduced.

Here, the reason why the fine BaZrO ₃ powder particles 32 are sufficiently dispersed in the BaTiO ₃ powder particles 31 will be described. When the state shown in FIG. 4, a plurality of BaTiO ₃ powder particles 31 adjacent during sintering directly contact hard with each other. Therefore, before the necking phenomenon between the BaTiO ₃ powder particles 31 occurs, the solid solution of the BaZrO ₃ powder particles 32 into the BaTiO ₃ powder particles 31 starts. This solid solution also promotes the solid solution of the rare earth element R, The formation of one region 12 proceeds early. In such a state, the BaTiO ₃ powder particles 31 that are adjacent during the sintering, that is, the possibility that the respective second regions 13 in the sintered main phase particles 11 are in contact with each other is reduced, and this contact is caused. The generation of the coarse second region 13 is suppressed.

If the average particle size of the second raw material powder, that is, BaZrO ₃ is larger than 1/3 of the average particle size of the first raw material powder, the BaZrO ₃ powder particles 32 in FIG. 4 are dispersed between the BaTiO ₃ powder particles 31. As a result, the D90 value in the diameter distribution of the second region 13 after sintering becomes as large as 0.25 μm or more, and the electrostriction of the dielectric ceramic cannot be reduced. In the case of less than 1/30, even if the BaZrO ₃ powder particles 32 are sufficiently dispersed, the particle size is small, so the distance between the BaTiO ₃ powder particles 31 is shortened, and the formation of the first region 12 is further reduced. Since there is an insufficient region, contact between the second regions 13 cannot be suppressed, and generation of the coarse second region 13 cannot be suppressed. Therefore, the D90 value becomes as large as 0.25 μm or more as in the case where it is larger than 1/3.

In addition, the above production method is characterized in that only the first raw material powder and the second raw material powder are first mixed and dispersed in the liquid, and then the third raw material powder is added to the liquid. If this is not performed and the first raw material powder, the second raw material powder, and the third raw material powder are mixed in the liquid at once, the BaZrO ₃ powder particles 32 in FIG. 4 cannot be sufficiently dispersed. The electrostriction of the dielectric ceramic cannot be reduced.

Furthermore, BaZrO ₃ as the second raw material powder is a compound that is particularly easily dissolved in the first raw material powder. If, for example, SrZrO _{3 is} used instead of BaZrO ₃ , the solid solution of the rare earth element R in the first raw material powder hardly progresses even if the above manufacturing method is performed, which also reduces the electrostriction of the dielectric ceramic. I can't.

  Note that the synthesis method of the first raw material powder and the second raw material powder is not a problem. For example, a solid phase method or a wet method such as an oxalic acid method, a hydrothermal method, or a coprecipitation method may be used.

Further, BaZrO ₃ used as the second raw material powder may be partially substituted with Hf, as described above.

  Furthermore, the dielectric ceramic of the present invention may contain inevitable impurities such as alkali metals, Cl, S, and P, as long as the object of the present invention is not impaired.

  Next, the analysis method of the microstructure of the dielectric ceramic of the present invention and the measurement of electric characteristics will be described.

  The dielectric ceramic of the present invention is cut to produce a thin piece having a thickness of about 0.1 μm, which is used as a sample for cross-sectional observation. This sample is observed with a transmission electron microscope (TEM), and the cross section of the ceramic is observed, and the average particle diameter of the main phase particles 11 is measured.

  The diameters of the first region 12 and the second region 13 are measured by using an energy dispersive X-ray microanalyzer (STEM-EDX) having a resolution of 3 nm or less equipped with Scanning-TEM. First, 50 main phase particles 11 are randomly extracted, and the concentration of the rare earth element R is analyzed by mapping. The first region 12 and the second region 13 are specified by the concentration difference of the rare earth element R in the mapping. In order to clarify the boundary line, the average value of the concentration of the rare earth element R is measured at any five points in the approximate center of the first region 12, and a line that is 1/3 of the average value in the mapping field of view. Is the boundary. That is, the region that is less than 1/3 of the average value is the second region 13.

  Electrostriction is obtained by measuring the amount of displacement when a sinusoidal AC electric field of 1 kHz / mm and 1 kHz is applied, and dividing the displacement by the effective thickness on which the electric field acts.

  Next, the present invention will be described more specifically based on examples. This example was carried out in order to provide a basis for limiting the scope of the present invention and to confirm the effect of these.

  Example 1 In this example, a multilayer ceramic capacitor in which the size of the second region was changed in a ceramic having a specific composition was produced, and the change in electrostriction due thereto was evaluated.

First, BaTiO ₃ powder synthesized by a solid phase method was prepared. The average primary particle size of the BaTiO ₃ powder was 0.20 μm, and the c / a axial ratio was 1.010. Similarly, BaZrO ₃ powders having various average primary particle sizes synthesized by a solid phase method were prepared. The primary particle size ratio of the BaZrO ₃ powder to the BaTiO ₃ powder at this time is as shown in Sample Nos. 1 to 12 in Table 1. Further, Gd ₂ O ₃ , MgO, MnO ₂ , SiO ₂ and BaCO ₃ powder were prepared.

The BaTiO ₃ powder and BaZrO ₃ powder were mixed in water for 24 hours using a partially stabilized zirconia media having a diameter of 1 mmφ to obtain a slurry in which the BaZrO ₃ powder was sufficiently dispersed in the BaTiO ₃ powder. . The amount of BaZrO _{3 with} respect to 100 mol parts of BaTiO ₃ was 10 mol parts.

Next, Gd ₂ O ₃ , MgO, MnO ₂ , SiO ₂ and BaCO ₃ powder in the slurry are respectively 4 mol parts, 4 mol parts, 0.3 mol parts with respect to 100 mol parts of BaTiO ₃ , 8 mol part and 1 mol part were added and further mixed for 4 hours.

  The obtained slurry was dried to obtain a dielectric ceramic raw material powder.

  A polyvinyl butyral binder and ethanol were added to the dielectric ceramic raw material powder and mixed by a ball mill to obtain a ceramic slurry. This ceramic slurry was formed into a sheet by a doctor blade method to obtain a ceramic green sheet.

  A conductive paste mainly composed of Ni was screen-printed on the surface of the ceramic green sheet to form a conductive paste layer for constituting internal electrodes. 150 ceramic green sheets on which the conductive paste layer was formed were stacked so that the side from which the conductive paste layer was drawn was alternated to obtain a stacked body.

This laminate was heated at 350 ° C. in a nitrogen atmosphere to burn the binder, and then in a reducing atmosphere consisting of H ₂ —N ₂ —H ₂ O gas and having an oxygen partial pressure of 10 ^−9.5 MPa. The ceramic laminated body which was hold | maintained for 60 minutes at the temperature shown to the sample numbers 1-12 of Table 1 and baked was obtained.

  External electrodes electrically connected to the internal electrodes by applying a conductive paste containing glass frit and containing Cu as a main component to both end faces of the ceramic laminate and baking at 800 ° C. in a nitrogen atmosphere. Formed. Furthermore, in order to improve solderability, a Ni plating layer and a Sn plating layer were formed on the external electrode.

The outer dimensions of the multilayer ceramic capacitors of Sample Nos. 1 to 12 thus obtained are 3.2 mm in length, 1.6 mm in width, and 1.2 mm in thickness, and the thickness of the ceramic layer interposed between the internal electrodes. Was 3 μm, the number of ceramic layers effective for electrostatic capacity was 150, and the counter electrode area per ceramic layer was 2.1 mm ² .

The samples Nos. 13 and 14 are different from the samples Nos. 1 to 12 in the manufacturing method. That is, the samples Nos. 13 and 14 are the same as the production method of Sample Nos. 1 to 12 in that BaTiO ₃ powder, BaZrO ₃ powder, Gd ₂ O ₃ , MgO, MnO ₂ , SiO ₂ and BaCO ₃ powder were simultaneously mixed for 4 hours. They are different and the other processes are the same.

Samples 15 and 16 differ from samples 1 to 12 in that SrZrO ₃ powder having an average primary particle size of 0.06 μm is used instead of BaZrO ₃ powder. The other steps are the same.

  As described above, evaluation samples of sample numbers 1 to 16 were obtained.

  First, the dielectric constants ε of sample numbers 1 to 16 were evaluated by measuring the electrostatic capacity at 25 ° C. under an alternating electric field of 1 kHz and 1 Vrms. As a temperature characteristic index, the rate of change in capacitance at 125 ° C. with respect to the capacitance at 25 ° C. was measured.

Next, a sine wave type AC electric field of V _0-P = 90 V and 1 kHz was applied to the samples of sample numbers 1 to 16, and the displacement in the thickness direction of the samples was measured. This displacement was divided by the total thickness of the ceramic layer effective for capacitance, and this was electrostrictive.

  Next, for samples 1 to 16, a cross-section including the central portion of the multilayer ceramic capacitor was prepared as a flaky analytical sample having a thickness of about 0.1 μm, and the particle size of 50 main phase particles was measured using TEM. The average particle diameter was determined. Further, a mapping analysis of rare earth elements was performed using STEM-EDX, and the diameters of the first region and the second region were measured. In all the samples, the average concentration of the rare earth element in the first region was three times or more than the average concentration of the rare earth element in the second region.

  Cumulative distribution curves for 50 diameters of the first region and the second region measured by the above method were prepared, and the respective D50 value and D90 value were calculated.

  The results are shown in Table 1. Sample numbers marked with * are outside the scope of the present invention. Moreover, the cumulative distribution curve of the diameter of the 2nd area | region of the sample number 3 and the sample number 14 is shown in FIG.

  Sample Nos. 1 to 6 and 8 to 10 had a D90 value of less than 0.25 μm in the second region, so that the electrostriction was as small as 0.055% or less, and the squeal was at a level where there was no problem in practical use.

In Sample No. 7, since the average primary particle size of BaZrO ₃ is less than 1/30 of BaTiO ₃ , the D90 value in the second region is 0.25 μm or more, and the electrostriction is as large as 0.062%.

In Sample Nos. 11 and 12, since the average primary particle size of BaZrO ₃ is larger than 1/3 of BaTiO ₃ , the D90 value in the second region is 0.25 μm or more, electrostriction is 0.058%, and 0.5. As large as 081%.

In Sample Nos. 13 and 14, BaTiO ₃ powder, BaZrO ₃ powder, Gd ₂ O ₃ , MgO, MnO ₂ , SiO ₂ and BaCO ₃ powder were mixed at the same time by a ball mill, so the D90 value in the second region was 0.25 μm. Thus, the electrostriction is large as 0.075% and 0.13%.

Sample No. 15 used SrZrO ₃ powder instead of BaZrO ₃ powder, so that sufficient sinterability was not obtained.

  Sample No. 16 was obtained by sintering the sample No. 15 at a higher firing temperature. The D90 value was 0.25 μm or more and the electrostriction was as large as 0.079%.

  Sample No. 6 is at a level where electrostriction is not a problem, but because the D50 value in the second region is less than 0.05 μm, the dielectric constant is low as 480 and the temperature characteristic is as low as −29.2%. It is not preferable.

  [Example 2] In this example, the composition of the dielectric ceramic is changed in various ways, and the effect of contributing to the various characteristics is observed.

First, BaCO _3, to prepare the _{SrCO 3, CaCO 3, TiO 2} , ZrO 2, so that the composition of Table _{2 (Ba 1-xy Ca x} Sr y) (Ti 1-z Zr z) O 3 After weighing, they were mixed by a ball mill, heat-treated at 1100 to 1200 ° C., and pulverized. This gave _{(Ba 1-xy Ca x Sr} y) (Ti 1-z Zr z) O 3 powder having an average primary particle diameter 0.1 to 0.3 [mu] m.

Obtained in the above _{(Ba 1-xy Ca x Sr} y) (Ti 1-z Zr z) O 3 powder 100 parts by mol relative to, a molar showing a BaZrO ₃ powder having an average primary particle diameter 0.03μm in Table 2 in addition parts, and mixed for 24 hours under the same conditions as in example 1 to give the _{(Ba 1-xy Ca x Sr} y) (Ti 1-z Zr z) O 3 powder BaZrO ₃ powder was thoroughly dispersed slurry .

Then, the above _{slurry, Gd 2 O 3, MgO,} SiO 2, V 2 O 3, of CuO and BaCO _{3 powder, (Ba 1-xy Ca x} Sr y) (Ti 1-z Zr z) O 3 As shown in Table 2, b mole part, c mole part, d mole part, 0.5 mole part, 0.5 mole part and 3 mole part were added to 100 mole parts, and mixed for 4 hours. The obtained slurry was dried to obtain a dielectric ceramic raw material powder.

A compact was produced from the dielectric ceramic raw material powder in the same manner as in Example 1. This laminate was heated at 350 ° C. in a nitrogen atmosphere to burn the binder, and then in a reducing atmosphere composed of H ₂ —N ₂ —H ₂ O gas and having an oxygen partial pressure of 10 ^−10.5 MPa. It was held at 1220 ° C. for 60 minutes to obtain a fired ceramic laminate.

  A multilayer ceramic capacitor serving as an evaluation sample was produced from the ceramic laminate through the same steps as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

  In all samples of sample numbers 17 to 41, the D90 value of the second region was less than 0.25 μm, and the electrostriction was 0.055% or less. However, a sample outside the desirable composition range as described below is not preferable in terms of dielectric constant or temperature characteristics.

  That is, Sample No. 18 having a Ca substitution amount x larger than 0.15 is not preferable because the dielectric constant is as low as 420.

  Sample Nos. 20 and 25 having an Sr substitution amount x greater than 0.15 are not preferable because their temperature characteristics are -36.8% and -24.6%.

  Sample numbers 25 and 29 in which 100z + a representing the total amount of Zr in the dielectric ceramic is greater than 0.30 have low dielectric constants of 230 and 320, and temperature characteristics of −24.6% and −23.5%. Bad and unfavorable.

The content of the rare earth element R is greater than 30 parts by mole with respect to _{(Ba 1-xy Ca x Sr} y) (Ti 1-z Zr z) O 3 100 molar parts, that is, the content b of Gd ₂ O ₃ Sample number 34 exceeding 15 is not preferable because the dielectric constant is as low as 330. Sample No. 30 where b is smaller than 2 is not preferable because the temperature characteristics are as bad as -33.2%.

  Sample No. 35 having an MgO content c of less than 1 is not preferable because its temperature characteristic is as bad as -35.5%. Sample number 38 with c exceeding 20 is not preferable because the dielectric constant is as low as 360 and the temperature characteristic is as low as −29.2%.

Sample No. 41 having a SiO ₂ content d greater than 15 is not preferable because the dielectric constant is as low as 470.

  [Example 3] In this example, in a specific dielectric ceramic composition, a multilayer ceramic capacitor in which only the kind of rare earth element was changed in various ways was manufactured, and changes in electrostriction, dielectric constant, and temperature characteristics caused thereby were measured. It has been evaluated.

First, BaTiO ₃ powder synthesized by a solid phase method was prepared. The average primary particle size of the BaTiO ₃ powder was 0.15 μm, and the c / a axial ratio was 1.008. Similarly, a BaZrO ₃ powder having an average primary particle size of 0.03 μm synthesized by a solid phase method was prepared. Furthermore, oxides of various rare earth elements shown in Table 3, MgO, MnO ₂ , SiO ₂ and BaCO ₃ powder were prepared.

Next, the BaTiO ₃ powder and the BaZrO ₃ powder were mixed under the same conditions as in Example 1 to obtain a slurry in which the BaZrO ₃ powder was sufficiently dispersed in the BaTiO ₃ powder. The amount of BaZrO _{3 with} respect to 100 mol parts of BaTiO ₃ was 6 mol parts.

Next, rare earth element oxides, MgO, MnO ₂ , SiO ₂ and BaCO ₃ powder shown in Table 3 are added to the slurry in an amount of 7 mole parts, 3 parts in terms of rare earth elements with respect to 100 mole parts of BaTiO ₃ , respectively. Mole parts, 0.6 mole parts, 6 mole parts and 0.5 mole parts were added and mixed for another 4 hours.

The obtained slurry was dried to obtain a raw material powder of a dielectric ceramic, and thereafter ^subjected to the same process as in Example 1, followed by reduction with an oxygen partial pressure of 10 ^−10.5 MPa made of H ₂ —N ₂ —H ₂ O gas. Was held at 1220 ° C. for 60 minutes in a neutral atmosphere to obtain a fired ceramic laminate. Thereafter, through the same process as in Example 1, a multilayer ceramic capacitor was produced, and samples Nos. 42 to 59 were obtained as evaluation samples.

  Table 3 shows the results of evaluating the same evaluation items under the same measurement conditions as in Example 1.

  In all samples of sample numbers 42 to 59, the D90 value in the second region was less than 0.25 μm, and the electrostriction was 0.055% or less. Further, a dielectric constant of 500 or more and temperature characteristics better than ± 22% were obtained. As described above, the dielectric ceramic of the present invention can achieve desired characteristics even in various rare earth elements.

1 is a cross-sectional view schematically showing a multilayer ceramic capacitor 1 according to an embodiment of the present invention. It is the figure which showed typically the cross section in the arbitrary surfaces of the dielectric ceramic of this invention. It is the figure which showed typically the cross section in the arbitrary surfaces of the dielectric material ceramic in the comparative example of this invention. In an embodiment of the dielectric ceramic manufacturing method of the present invention, the state in which BaTiO ₃ powder particles and BaZrO ₃ powder particles were sufficiently dispersed, a diagram schematically showing. It is a figure which shows the cumulative distribution curve in the distribution of the diameter of the 2nd area | region of the sample numbers 3 and 14 of Example 1. FIG.

Explanation of symbols

1 multilayer ceramic capacitor 3 dielectric ceramic layers 4 and 5 the internal electrodes 8 and 9 the external electrode 11, 21 the main phase grains 12, 22 first regions 13, 23 second region 31 of the BaTiO ₃ powder particles 32 BaZrO ₃ powder particles

Claims (5)

_{(Ba 1-xy Ca x Sr} y) (Ti 1-z Zr z) O 3 ( however, 0 ≦ x + y ≦ 0.15,0 ≦ z ≦ 0.3) includes, and the (Ba _1-xy Ca _x Sr _y) (relative to _{Ti 1-z Zr z) O} 3 100 molar parts, the rare earth element R (Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm , Yb, Lu) in a dielectric ceramic having a composition comprising 4 to 30 mol parts and 2 to 30 mol parts of BaZrO ₃ (where the total value with 100z does not exceed 30) ,
Wherein the dielectric ceramic main phase particles, a solid solution composed of the _{(Ba 1-xy Ca x Sr} y) (Ti 1-z Zr z) O 3 , and perovskite structure containing the rare earth element R,
The main phase particles are composed of two regions, that is, a first region where the concentration of the rare earth element is high and a second region where the concentration of the rare earth element is low, and the average concentration of the rare earth element in the first region is The molar ratio of the rare earth element in the second region is not less than 3 times, and
When the cross section of the dielectric ceramic is observed, the D90 value in the diameter distribution of the second region is less than 0.25 μm. When said cross section is observed, the D50 value in the distribution of the diameter of the second region is 0.05μm or more, the dielectric ceramic of claim 1. The dielectric ceramic according to claim 1 or 2 , comprising 1 to 20 mol parts of Mg and 1 to 15 mol parts of Si with respect to 100 mol parts of the ABO ₃ . _{(Ba 1-xy Ca x Sr} y) (Ti 1-z Zr z) O 3 ( however, 0 ≦ x + y ≦ 0.15,0 ≦ z ≦ 0.3) includes, and the (Ba _1-xy Ca _x Sr _y) (relative to _{Ti 1-z Zr z) O} 3 100 molar parts, the rare earth element R (Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm , Yb, Lu) 4-30 mol parts, BaZrO ₃ 2-30 (however, the total value with 100z does not exceed 30) mol dielectric , and a method for producing a dielectric ceramic having a composition Because

_{(Ba 1-xy Ca x Sr} y) (Ti 1-z Zr z) O 3 ( however, 0 ≦ x + y ≦ 0.15,0 ≦ z ≦ 0.3) first raw material powder mainly composed of, Preparing a second raw material powder mainly composed of BaZrO ₃ and a third raw material powder containing at least a rare earth compound;
Step of mixing and dispersing the first raw material powder and the second raw material powder in a liquid, and then adding, mixing and drying the third raw material powder in the liquid to obtain a fourth raw material powder When,
A method for producing a dielectric ceramic comprising a step of forming and firing the raw material powder 4,
The method for producing a dielectric ceramic, wherein an average primary particle size of the second raw material powder is 1/30 to 1/3 of an average primary particle size of the first raw material powder. In a laminated ceramic capacitor comprising a plurality of laminated dielectric ceramic layers, internal electrodes disposed between the dielectric ceramic layers, and external electrodes electrically connected to the internal electrodes,
A multilayer ceramic capacitor, wherein the dielectric ceramic layer is formed of the dielectric ceramic according to any one of claims 1 to 3 .