JP6034111B2 - Capacitor - Google Patents

Description

  The present invention relates to a capacitor using a dielectric ceramic composed of crystal particles mainly composed of barium titanate as a dielectric layer.

  In recent years, with the development of high-luminance blue light-emitting diodes (LEDs), the development of lighting equipment that uses LEDs as light sources has rapidly progressed along with full-color LED display devices that can achieve high visibility. It's getting on.

  In such an electronic device using an LED, a method of generating a DC voltage for driving the LED from a commercial power source using an AC-DC converter is adopted. However, the AC-DC converter uses a commercial power source (100V). ) Is a circuit that drives a LED by generating a desired DC output voltage from the AC voltage, and a rectifier circuit used in such a circuit is equipped with a capacitor together with a field effect transistor (MOSFET) as a control circuit element (For example, refer to Patent Document 1).

  However, in an electronic device using such an LED, since the applied voltage is high and the temperature change due to heat generation during light emission is large, the capacitance is high even when a voltage is applied as a capacitor. (Hereinafter, expressed as a relative dielectric constant) that can be maintained is required.

JP 2011-35112 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a capacitor capable of maintaining a high capacitance even when a voltage is applied at a high temperature.

The capacitor of the present invention comprises a dielectric ceramic containing crystal particles mainly composed of barium titanate and containing at least one rare earth element (RE) selected from the group of terbium, dysprosium, holmium, erbium and gadolinium. It comprises a dielectric layer, wherein the crystal grains, at the position of depth 20nm from the grain boundary, and crystal particle concentration of the first crystal group which is 0 to 0.5 atomic% of the rare earth element (RE) a high concentration of the rare earth element (RE) than the crystal grains of the first crystal group, and a crystal grain of the second crystal group concentration is a 0.3-0.9 atomic%, the second 1 Ri said difference is 0.1 atomic% to 0.7 atomic% der following concentrations of the rare earth element (RE) of the crystal group of crystal grains and the second crystal group of crystal grains, of the second crystal group Crystal grains are of the first crystal group. The average particle diameter is larger than that of crystal grains . Hereinafter, the “first crystal group” and the “second crystal group” may be referred to as “first crystal group” and “second crystal group”, respectively.

  According to the present invention, it is possible to obtain a capacitor capable of maintaining a high capacitance even when a voltage is applied at a high temperature.

(A) is a schematic sectional drawing which shows an example of the capacitor | condenser of this invention, (b) is an enlarged view of the dielectric material layer which comprises the capacitor | condenser of FIG. 1, and is the schematic diagram which shows a crystal grain and a grain boundary phase It is. (A) is a schematic diagram showing the concentration gradient of the crystal grains constituting the first crystal group and the rare earth element (RE) therein, and (b) is the crystal grains constituting the second crystal group. It is a schematic diagram showing the concentration gradient of the rare earth element (RE) inside.

  The capacitor of this embodiment will be described in detail based on the schematic cross-sectional view of FIG. FIG. 1A is a schematic cross-sectional view showing an example of the capacitor of the present invention, and FIG. 1B is an enlarged view of a dielectric layer constituting the capacitor of FIG. 1, showing crystal grains and grain boundary phases. It is a schematic diagram. FIG. 2A is a schematic diagram showing the concentration gradient of the crystal grains constituting the first crystal group and the rare earth element (RE) therein, and FIG. 2B is the crystal constituting the second crystal group. It is a schematic diagram showing the density | concentration gradient of particle | grains and the rare earth element (RE) inside it.

  In the capacitor of this embodiment, external electrodes 3 are formed at both ends of the capacitor body 1. The external electrode 3 is formed, for example, by baking Cu or an alloy paste of Cu and Ni.

  The capacitor body 1 is configured by alternately laminating dielectric layers 5 made of dielectric ceramics and internal electrode layers 7. In FIG. 1, the laminated state of the dielectric layer 5 and the internal electrode layer 7 is shown in a simplified manner. However, the capacitor of the present invention includes a laminated body having several hundreds of dielectric layers 5 and internal electrode layers 7. It has become.

  The dielectric layer 5 made of a dielectric ceramic is composed of crystal grains 9 and a grain boundary phase 11, and the average thickness is preferably 5 μm or less, particularly 3 μm or less. Can be realized. The average thickness of the dielectric layer 5 is preferably 1 μm or more from the viewpoint of reducing variation in capacitance, stabilizing capacitance-temperature characteristics, and improving high-temperature load life.

  The internal electrode layer 7 is preferably a base metal such as nickel (Ni) or copper (Cu) in that the manufacturing cost can be suppressed even when the number of layers is increased, and in particular, the dielectric layer 5 constituting the capacitor of the present embodiment Of these, nickel (Ni) is more desirable in that it can be fired simultaneously.

  The dielectric ceramic constituting the dielectric layer 5 in the capacitor of this embodiment includes crystal particles 9 mainly composed of barium titanate, and at least one selected from the group of terbium, dysprosium, holmium, erbium, and gadolinium. Contains rare earth elements (RE). Here, the crystal particle 9 containing barium titanate as a main component is the main crystal particle, and the main peak derived from barium titanate on the X-ray diffraction pattern obtained by X-ray diffraction. Is higher than the diffraction intensity of the main peak of the crystal phase other than barium titanate.

The crystal grains 9 are composed of at least two kinds of crystal grains having a difference in the rare earth element (RE) concentration of 0.1 atomic% or more and 0.7 atomic% or less at a depth of 20 nm from the grain boundary. It has been configured.

  Thereby, even if the capacitor is exposed to a high temperature and a DC voltage is applied, a capacitor with a small decrease in capacitance can be obtained. For example, when the capacitance measured under the condition that a DC voltage is not applied at room temperature (25 ° C.) is used as a reference, the rate of change in capacitance when a DC voltage of about 25 V is applied at 125 ° C. ( Hereinafter, it is referred to as a high temperature DC bias characteristic) within 73%. In the following description, when describing the characteristics, the relative permittivity may be used instead of the capacitance.

The dielectric ceramic in the present embodiment includes at least two kinds of at least one rare earth element (RE) selected from the group of terbium, dysprosium, holmium, erbium, and gadolinium in different amounts in the crystal grains 9a and 9b. The crystal particles 9a of the first crystal group have a rare earth element (RE) concentration contained in the crystal particles 9 of the first crystal group 9a and 9b. Since it is low, rare earth elements (RE) are scarcely dissolved in the central portion of the crystal grain 9a, and therefore, a tetragonal crystal phase with few additive components is dominant in the central portion. Therefore, a dielectric ceramic having a high relative dielectric constant can be obtained.

  On the other hand, since the concentration of the rare earth element (RE) contained in the crystal particles 9 is high in the crystal particles 9b of the second crystal group, the rare earth elements (RE) are dissolved in the deep portion inside the crystal particles 9b. Therefore, the crystal particle 9b has fewer defects such as oxygen vacancies than the crystal particle 9a, and the voltage dependency of the relative permittivity is reduced while maintaining a high relative permittivity. Is possible.

  It is difficult to reduce the rate of change of the dielectric constant when a DC voltage is applied to the crystal particles 9a alone. However, if the crystal particles 9b coexist with the crystal particles 9a, the crystal particles 9b originally have a relative dielectric constant. Due to the fact that the voltage dependency of the rate can be reduced, the rate of change of the relative dielectric constant when a DC voltage is applied can be reduced.

  On the other hand, there is no difference in the concentration of the rare earth element (RE) contained in the crystal grains 9 constituting the dielectric ceramic, and the concentration of the rare earth element (RE) at a depth of 20 nm from the grain boundary is 0. When it is composed of a group of crystal grains that cannot find a difference of 1 atomic% or more, when the capacitance measured under the condition that a DC voltage is not applied at room temperature (25 ° C.) is used as a reference, At 125 ° C., the rate of change in capacitance when a DC voltage of about 25 V is applied is greater than 73%.

  In this dielectric ceramic, terbium, dysprosium, holmium, erbium and gadolinium are selected as the rare earth elements (RE) to be included, but these rare earth elements (RE) are rare earth elements (RE) in the periodic table. This is because it is easy to dissolve in the crystal particles 9 mainly composed of barium titanate. Then, by dissolving these rare earth elements (RE) in the crystal particles 9 to form two kinds of crystal particles 9a and 9b having different concentrations of the rare earth elements (RE) in the dielectric ceramic, The withstand voltage characteristics of the porcelain can be changed.

Next, vanadium, magnesium, manganese, and yttrium are included in this dielectric ceramic, and the content of each element is determined in terms of V ₂ O ₅ with respect to 100 moles of titanium constituting barium titanate. 0.05-0.20 mol, yttrium 0.5-2.0 mol in terms of Y ₂ O ₃ , magnesium 1.0-3.0 mol in terms of MgO, and manganese 0.22-0 in terms of MnO .50 moles and rare earth elements (RE) in the range of 0.65 to 2.80 moles in terms of RE ₂ O ₃ , and crystal grains 9 having different rare earth element (RE) concentrations are 20 nm deep from the grain boundaries. In the range, the concentration of the rare earth element (RE) is 0.02 to 0.42 atomic%, the first crystal group of crystal particles 9a, and the rare earth element (RE) concentration is 0.45 to 0.70 atomic%. A second crystal Among these crystal particles 9a and 9b, the average particle size of the crystal particles 9a of the first crystal group is 0.10 to 0.18 μm, and the crystal particles of the second crystal group The average particle size of 9b is 0.2 to 0.5 μm, and the constituent ratio of the crystal particles 9a of the first crystal group and the crystal particles 9b of the second crystal group is set to a unit area of the polished surface of the dielectric ceramic. The ratio b / (a + b) is 0.4 to 0.7 when the area of the crystal grain 9a seen at the time is a and the area of the crystal grain 9b is b.

When the dielectric ceramic is configured as described above, in addition to the high-temperature DC bias characteristics,
A capacitor having a high relative dielectric constant, a low relative dielectric constant temperature change rate, and an excellent high temperature load life can be obtained. For example, the relative dielectric constant at room temperature (25 ° C.) is 2000 or more, and the rate of change of the relative dielectric constant when the room temperature (25 ° C.) is the reference in the temperature range of −55 to 125 ° C. The temperature characteristic is within ± 13.8% (the rate of change in the dielectric constant at 125 ° C. is the largest between −55 and 125 ° C., and hence the rate of change at 125 ° C. is shown below). In addition, the change rate of the relative permittivity measured with a DC voltage applied at 125 ° C. is −51 .5 with respect to the relative permittivity measured with no DC voltage applied at 25 ° C. (no load state). It can be within 8% (in a direction approaching NPO (± 0%)), and the high temperature load life evaluated under the condition of applying a DC voltage of 170 ° C. and 170 V can be 34 hours or more. Hereinafter, the term “high temperature load life” refers to the high temperature load life evaluated under the above conditions.

  When a predetermined amount of each of magnesium, manganese and yttrium is contained in the dielectric ceramic in addition to rare earth elements (RE), these elements are dissolved in the vicinity of the surface of the crystal particles 9, and Since it becomes possible to make the crystal grains 9 having a core-shell structure in the portion, it is possible to obtain a dielectric ceramic having a small relative dielectric constant temperature change rate as well as an increase in the relative dielectric constant. In the core-shell structure, in the X-ray diffraction pattern, for example, a diffraction peak (index is an overlap of 200, 020, 002) due to a cubic system between a diffraction peak of 200 planes and a diffraction peak of 002 planes. The cubic diffraction peak has a diffraction intensity comparable to that of the 200-plane diffraction peak and the 002-plane diffraction peak due to the tetragonal system.

  On the other hand, since the concentration of the rare earth element (RE) contained in the crystal particle 9 is high, the crystal particle 9b is in a state where the rare earth element (RE) is in a solid solution deep inside the crystal particle 9b. For this reason, the crystal particles 9b have reduced defects such as oxygen vacancies as compared with the crystal particles 9a. For this reason, the voltage dependence of the relative permittivity is reduced while maintaining a high relative permittivity. It becomes possible. Also, the high temperature load life can be increased.

  In this dielectric ceramic, a diffraction peak attributed to the first crystal particle having a core-shell structure and a diffraction peak attributed to the second crystal particle having a large amount of additive components appear simultaneously. Here, the diffraction peak attributed to the first crystal particle and the diffraction peak attributed to the second crystal particle have different lattice constants due to the different solubility of the additive component.

  Further, as shown in FIGS. 2 (a) and 2 (b), the crystal particles 9a and 9b constituting the dielectric ceramic have different rare earth element (RE) concentration gradients, and crystals of the first crystal group. It is preferable that the particle 9a is 0.05 to 0.20 atomic% / nm and the crystal particle 9b of the second crystal group is 0.03 atomic% / nm or less.

  In addition, the dielectric ceramic according to the present embodiment can increase the dielectric constant because the average particle diameter of the crystal particles 9b is larger than the average particle diameter of the crystal particles 9a.

  As a result, the capacitor according to the present embodiment has a relative dielectric constant of 2000 or more at room temperature (25 ° C.), particularly at a relative dielectric constant measured at 25 ° C. with no DC voltage loaded (no load state). On the other hand, the rate of change in relative permittivity when DC voltage is applied at 125 ° C. (hereinafter referred to as a high temperature load state) can be made within −51.8%, and the reliability of the high temperature load life is excellent. It becomes a thing.

In this dielectric porcelain, yttrium (Y) contained separately from the rare earth element (RE) is an element that is less soluble in barium titanate than elements such as terbium, dysprosium, holmium, erbium, and gadolinium. It is. For this reason, yttrium can be dissolved in the vicinity of the surface of the barium titanate crystal particles 9, and thus the relative permittivity of the dielectric ceramic, the temperature change rate of the relative permittivity in the no-load state and the high-temperature load state, and the high temperature The reliability of the load life can be controlled. In this case, the concentration gradient of yttrium is preferably 0.05 to 0.20 atomic% / nm for both the crystal particles 9a and 9b.

  Here, regarding the concentration and concentration distribution of the rare earth element (RE) in the crystal particles 9, after the cross section of the dielectric ceramic is polished, the crystal particles are approximately on the image displayed on the monitor attached to the transmission electron microscope. Draw 30 circles, select crystal particles in and around the circle, and perform elemental analysis using a transmission electron microscope equipped with elemental analysis equipment. The crystal particles 9 to be selected at this time are obtained by calculating the area of each particle by image processing from the outline, and calculating the diameter when replaced with a circle having the same area. The diameter of the obtained crystal particle 9 is approximately 0.08. The crystal grain 9 is in the range of ˜0.60. The spot size of the electron beam when the analysis is performed is 0.5 to 2 nm, and the location to be analyzed is a position 20 nm (± 1 nm) deep from the grain boundary of the crystal grain 9.

  When the concentration of rare earth element (RE) in the crystal particle 9 is obtained, an electron beam is applied to the center of the crystal particle 9 and the amount of main elements contained in the crystal particle 9 is determined from the output of the obtained X-ray. It is determined as 100 atomic%, and the ratio of rare earth elements (RE) is determined from this. Here, examples of main elements include barium (Ba), titanium (Ti), vanadium (V), magnesium (Mg), manganese (Mn), and rare earth elements (RE). Thereafter, the concentration of the rare earth element (RE) is determined for each crystal particle 9, thereby determining the crystal particles 9a of the first crystal group and the crystal particles 9b of the second crystal group.

Next, when determining the concentration gradient of the rare earth element (RE), the points are located at substantially equal intervals on a straight line drawn toward the center in the range from the vicinity of the grain boundary to the center position of the central part, and near the grain boundary is obtained from the values analyzed in approximately 20nm and 200nm in depth from the grain boundary (referred to as _{d G} in FIG. 2 (a) (b)) . In this case, a value obtained by subtracting the rare earth element (RE) concentration at a depth of 19 to 21 nm and 195 to 205 nm from the concentration of the rare earth element (RE) at the grain boundary (0 to 1 nm) of the crystal grain 9 (concentration of the rare earth element). ) Is divided by the distance of the analyzed range (for example, 20 nm-0 nm = 20 nm, 200 nm-0 nm = 200 nm) to obtain a concentration gradient.

  As described above, the capacitor of the present embodiment includes the crystal particles 9a constituting the first crystal group and the crystal particles 9b constituting the second crystal group as the crystal particles 9. Where b / (a + b) where a represents the area of the crystal grains 9a constituting the first crystal group and b represents the area of the crystal grains 9b constituting the second crystal group. ) Is 0.4 to 0.7, and the average grain sizes of the crystal grains 9a constituting the first crystal group and the crystal grains 9b constituting the second crystal group are 0.10 to 0.18 μm, respectively. And 0.2 to 0.5 μm is desirable.

  Here, the average particle diameter of each of the crystal grains 9a constituting the first crystal group and the crystal grains 9b constituting the second crystal group is determined on the polished surface obtained by polishing (ion milling) the cross section of the dielectric ceramic. The diameter when the image displayed by the transmission electron microscope is taken into a computer, the contours of the crystal particles present on the image are processed, the area of each particle is obtained, and replaced with a circle with the same area. Is calculated from the average value of the calculated 30 crystal grains. In this case, the crystal particles 9a and 9b are distinguished from each other based on the result of previously determining the concentration gradient of the rare earth element (RE) from the crystal particles 9, and the average values of the crystal particles 9a and 9b are obtained by respectively determining the average values. Obtain the particle size.

Further, the area ratio of the crystal grains 9b constituting the second crystal group to the total area of the crystal grains 9a constituting the first crystal group constituting the dielectric ceramic and the crystal grains 9b constituting the second crystal group. Is calculated using the data used to determine the average particle size.

  In the capacitor of this embodiment, it is desirable that the crystal particles 9 constituting the dielectric ceramic are barium titanate crystal particles. When the crystal particle 9 does not contain calcium or the like (the calcium concentration in the crystal particle is less than 0.1 atomic%), a dielectric ceramic having a smaller dielectric loss (dielectric loss tangent) can be obtained.

  In addition, the crystal particles 9 constituting the dielectric porcelain include a first crystal particle having a calcium concentration of less than 0.3 atomic% in the crystal particle and a calcium concentration in the crystal particle of 0.3 atomic% or more. A composite particle having certain second crystal particles is preferable. When the crystal particles 9 are formed of the composite particles as described above, the temperature change rate of the relative dielectric constant under the condition that the dielectric loss is small and no DC voltage is applied can be reduced.

  Furthermore, the dielectric porcelain is 0.30 to 0.50 mol of manganese in terms of MnO with respect to 100 mol of titanium constituting barium titanate, and b / (a + b) is 0.4 to 0.6. If it is, the temperature change rate of the dielectric constant in a high temperature load state can be made into 51.5% (-51.5%) or less.

  Furthermore, when the crystal particles 9a and 9b contain calcium, and the concentration of the calcium is 9 mol% or less and 0.1 to 9.0 mol%, the dielectric loss of the dielectric ceramic is further reduced. Is possible.

  Regarding the concentration of calcium in the crystal particles 9a and 9b, elemental analysis is performed on the crystal particles present on the polished surface obtained by polishing the cross section of the dielectric ceramic using a transmission electron microscope provided with an elemental analysis device. At this time, the spot size of the electron beam is set to 5 nm or less, and the site to be analyzed is the central portion of the crystal particles 9a and 9b. Ba, Ti, Ca, V, Mg, Y, RE (rare earth element) and Mn detected by the analysis The ratio of calcium when the total amount of is 100% is determined. The crystal particles 9a and 9b to be analyzed are selected by drawing a circle containing about 10 crystal particles in the substantially central portion shown on the monitor (photograph) for microscopic observation. The center part of the crystal grains 9a and 9b is the center of a circle drawn along the outline of each crystal grain.

  Further, in the case of the capacitor according to the present embodiment, when the rare earth element (RE) contained in the dielectric ceramic is gadolinium (Gd), compared with the case where other rare earth elements (RE) are used, the no-load state and the high temperature are increased. While the temperature change rate of the relative permittivity in the loaded state can be reduced, the relative permittivity and the high temperature load life at room temperature (25 ° C.) can be improved.

  Further, in the capacitor according to the present embodiment, other components may be included in addition to the above-described components as long as desired dielectric characteristics can be maintained. For example, a glass component as an auxiliary agent for enhancing sinterability. And other additive components can be contained in the dielectric ceramic in a proportion of 0.5 to 2% by mass.

Next, a method for manufacturing the capacitor of the present embodiment will be described. However, the manufacturing method described below is an example, and the method is not limited to this method. First, as raw material powder, barium titanate powder (purity is 99% by mass or more, hereinafter referred to as BT powder) or barium calcium titanate powder in which calcium is dissolved in barium titanate (purity is 99% by mass or more, below) , BCT powder) or a mixed powder of BT powder and BCT powder (hereinafter, BT powder, BCT powder and mixed powder may be collectively referred to as raw material powder). In this case, the BCT powder is a perovskite-type barium titanate in which a part of the Ba site of barium titanate is substituted with Ca, and is represented by the chemical formula (Ba _1-x Ca _x ) TiO ₃ . In the present invention, the amount of Ca substitution in the Ba site is X = 0.0.
It is good that it is 1-0.05.

Further, as additives, _Tb 4 _{O 7} powder, _Dy 2 _{O 3} powder, _Ho 2 _{O 3} powder, to prepare at least one selected from _Er 2 _{O 3} powder and _Gd 2 _{O 3} powder group.

The average particle diameter of the raw material powder is preferably 0.10 to 0.35 μm, particularly 0.15 to 0.30 μm. The additive Tb ₄ O ₇ powder, Dy ₂ O ₃ powder, Ho ₂ O ₃ powder, Er ₂ O ₃ powder and Gd ₂ O ₃ powder also have an average particle size equal to or less than that of the raw material powder. Is preferably used.

In addition, for the reason of further improving the dielectric characteristics, V ₂ O ₅ powder, MgO powder, MnCO ₃ powder and Y ₂ O ₃ powder are prepared as additives in some cases. Also in this case, the average particle diameter is preferably equal to or less than that of the raw material powder.

  Next, a slurry is prepared using these raw material powders. When the capacitor of the present embodiment is manufactured, the second crystal group after firing out of the total amount of the raw material powders used for forming the dielectric ceramic. The amount corresponding to the ratio of forming the crystal particles 9b is divided in advance, and the molar ratio corresponding to the ratio of the subdivided raw material powder among the rare earth element (RE) oxide powder added to the subdivided raw material powder. The rare earth element (RE) is added and coating is performed. The coating process is performed by calcining at a temperature of 450 to 800 ° C. after mixing a predetermined amount of raw material powder and rare earth element (RE) oxide powder.

Next, a raw material powder coated with a rare earth element (RE) oxide powder (hereinafter referred to as a coating powder), a remaining raw material powder not coated with a rare earth element (RE) oxide powder, A dielectric powder is prepared by adding a predetermined amount of each of rare earth element (RE) oxide powder and additive powders such as V ₂ O ₅ powder, MgO powder, MnCO ₃ powder, and Y ₂ O ₃ powder.

  Next, a ceramic slurry is prepared by adding a special organic vehicle to the dielectric powder prepared as described above, and then a ceramic green sheet is formed using a sheet forming method such as a doctor blade method or a die coater method. To do. In this case, the thickness of the ceramic green sheet is preferably 1 to 6 μm from the viewpoint of reducing the thickness of the dielectric layer 5 to increase the capacity and maintaining high insulation.

  Next, a rectangular internal electrode pattern is printed and formed on the main surface of the obtained ceramic green sheet. Ni, Cu, or an alloy powder thereof is suitable for the conductor paste that forms the internal electrode pattern.

  Next, stack the desired number of ceramic green sheets with internal electrode patterns, and stack multiple ceramic green sheets without internal electrode patterns on the top and bottom so that the upper and lower layers are the same number. Form the body. In this case, the internal electrode pattern in the sheet laminate is shifted by a half pattern in the longitudinal direction.

  Next, the sheet laminate is cut into a lattice shape to form a capacitor body molded body so that the end of the internal electrode pattern is exposed. By such a laminating method, the internal electrode pattern can be formed so as to be alternately exposed on the end surface of the cut capacitor body molded body.

  Next, the capacitor body molded body is degreased and fired. The firing temperature is preferably 1200 to 1300 ° C. because the solid solution of the additive in the BCT powder and the coating powder and the grain growth of the crystal particles are suppressed in this embodiment.

  Moreover, after baking, it heat-processes in a weak reducing atmosphere again. This heat treatment is performed to reoxidize the dielectric ceramic reduced in firing in a reducing atmosphere and recover the insulation resistance reduced and reduced during firing. The temperature is preferably 900 to 1100 ° C. for the purpose of increasing the amount of reoxidation while suppressing the grain growth of the crystal grains 9. In this way, a dielectric ceramic having a small relative dielectric constant temperature change rate can be obtained even in a high temperature load state.

  Next, an external electrode paste is applied to the opposing ends of the capacitor body 1 and baked to form the external electrodes 3. Further, a plating film may be formed on the surface of the external electrode 3 in order to improve mountability.

  Hereinafter, although an example is given and a capacitor of the present invention is explained in detail, the present invention is not limited to the following examples.

First, BT powder, BCT powder, and a mixed powder of BT powder and BCT powder were prepared as raw material powder. Further, as additives, V ₂ O ₅ powder, MgO powder, MnCO ₃ powder, Y ₂ O ₃ powder, Tb ₄ O ₇ powder, Dy ₂ O ₃ powder, Ho ₂ O ₃ powder, Er ₂ O ₃ powders and at least one rare earth element (RE) oxide powder selected from the group of Gd ₂ O ₃ powder (hereinafter referred to as rare earth element oxide powder) were prepared. Next, these various powders were mixed by the following procedure to prepare the dielectric powder so that the composition finally had the ratios shown in Tables 1 and 2. These raw material powders having a purity of 99.9% by mass were used. The raw material powder having an average particle size of 0.2 μm was used. V ₂ O ₅ powder, MgO powder, MnCO ₃ powder, Y ₂ O ₃ powder, and rare earth element oxide powder having an average particle diameter of about 0.1 μm were used. The Ba / Ti ratio of the BCT powder was set to 1.

  When preparing a powder in which a rare earth element oxide powder is applied to a raw material powder by coating (hereinafter referred to as a coating powder), the dielectric material is used out of the total amount of the raw material powder and the rare earth element oxide powder to be used. The amount of the raw material powder corresponding to the proportion of the crystal particles of the second crystal group formed in the porcelain and the proportion of the rare earth element oxide powder corresponding to the proportion of the subdivided raw material powder are respectively weighed. Were mixed using a ball mill, and then placed in a ceramic container and subjected to heat treatment at 500 ° C. for 1 hour. A coated powder was thus prepared.

Next, the remaining raw material powder, the remaining rare earth element oxide powder, the V ₂ O ₅ powder, the MgO powder, the MnCO ₃ powder, and the Y ₂ O ₃ powder are added to the coating powder to form a dielectric. Body powder was prepared. In this case, the mixing ratio of the coating powder to the raw material powder not coated with the rare earth element (RE) oxide is such that the coating powder corresponds to the crystal particles of the second crystal group and the raw material powder is the first powder. The b / (a + b) ratios in Tables 3 and 4 were set so as to correspond to the crystal grains of the crystal group.

As the sintering aid, glass powder having a composition of SiO ₂ = 55, BaO = 20, CaO = 15, and Li ₂ O = 10 (mol%) was used. The addition amount of the glass powder was 1 part by mass with respect to 100 parts by mass of the BCT powder.

  Next, these raw material powders were wet mixed by adding a mixed solvent of toluene and alcohol as a solvent using zirconia balls having a diameter of 5 mm. A polyvinyl butyral resin and a mixed solvent of toluene and alcohol were added to the wet-mixed powder, and wet-mixed using a zirconia ball having a diameter of 5 mm to prepare a ceramic slurry. A ceramic green sheet having a thickness of 2 μm was prepared by a doctor blade method. .

A plurality of rectangular internal electrode patterns mainly containing Ni were formed on the upper surface of the ceramic green sheet. The conductor paste used for the internal electrode pattern was Ni powder having an average particle size of 0.3 μm, and 30 parts by mass of BCT powder used for a green sheet as a co-material with respect to 100 parts by mass of Ni powder.

Next, 300 ceramic green sheets on which internal electrode patterns were printed were laminated, and 20 ceramic green sheets on which the internal electrode patterns were not printed were laminated on the upper and lower surfaces, respectively, using a press machine at a temperature of 60 ° C. and pressure Lamination was performed under the conditions of 10 ⁷ Pa and time 10 minutes, and cut into predetermined dimensions to form a laminated molded body.

The obtained laminated molded body was subjected to binder removal treatment at 300 ° C. in the atmosphere at a temperature rising rate of 10 ° C./h, heated at the same temperature rising rate, and then heated from 500 ° C. to 300 ° C./h. Then, after baking at 1250 ° C. for 2 hours in hydrogen-nitrogen, and then cooling to 1000 ° C. at a temperature drop rate of 300 ° C./h, heat treatment (reoxidation treatment) is performed at 1000 ° C. for 4 hours in a nitrogen atmosphere. The capacitor body was manufactured by cooling at a temperature decrease rate of 300 ° C./h. The size of the capacitor body is a size of a multilayer ceramic capacitor that is compatible with the 3216 type. The average thickness of the dielectric layer was 3.6 μm, and the effective area of one internal electrode layer was 3.54 mm ² . Here, the effective area is an area where internal electrode layers formed so as to be exposed at end faces in different directions of the capacitor body overlap.

Sample No. 36 and sample no. No. 93 was prepared by post-adding the whole amount of the rare earth oxide powder (no coating used). Sample No. 37 and Sample No. No. 94 is a coating powder prepared by mixing the total amount of rare earth element oxide powder and the total amount of raw material powder, to which V ₂ O ₅ powder, MgO powder, MnCO ₃ powder, and Y ₂ O ₃ powder are prepared. And a sintering aid. Sample No. 38 and Sample No. No. 95 is prepared by mixing a coating powder prepared using a raw material powder having an average particle size of 0.1 μm and a raw material powder having an average particle size of 0.45 μm. Sample No. 39 and sample no. 96 is used as a raw material powder for preparing a coating powder having an average particle size of 0.2 μm, and is added as a raw material powder (crystal particles corresponding to the crystal particles of the first crystal group in Tables 1 and 2). The one with a diameter of 50 nm is used. Sample No. Nos. 40, 41, and 46 to 48 are obtained by changing the heating rate from 500 ° C. to the maximum temperature during the main firing. 40 is 1000 ° C./h, sample no. 41 is 1500 ° C./h. 46 is 1300 ° C./h. 47 is 150 ° C./h and sample no. 48 is 1900 ° C./h. Sample No. Nos. 97, 98, and 103 to 105 are obtained by changing the heating rate from 500 ° C. to the maximum temperature during the main firing. 97 is 1000 ° C./h. 98 is 1500 ° C./h. 103 is 1300 ° C./h. 104 is 150 ° C./h and sample no. 105 is 1900 degrees C / h.

  Sample No. Nos. 49 and 106 are raw material powders having an average particle diameter of 50 nm as raw material powders to be coated powders.

  Sample No. Nos. 50 to 53 are obtained by changing the calcining temperature when preparing the coating powder. 50 is 450 ° C., sample no. 51 is 650 ° C., sample No. 52 is 300 ° C. and sample no. 53 is 950 degreeC.

  Sample No. Nos. 107 to 110 are also obtained by changing the calcining temperature when preparing the coating powder. No. 107 is 450 ° C., sample no. No. 108 is 650 ° C., sample no. 109 is 300 ° C. and sample no. 110 is 950 degreeC.

Next, the fired capacitor body was barrel-polished, and then an external electrode paste containing Cu powder and glass was applied to both ends of the capacitor body and baked at 850 ° C. to form external electrodes. Thereafter, using an electrolytic barrel machine, Ni plating and Sn plating were sequentially performed on the surface of the external electrode to produce a multilayer capacitor.
<Evaluation>
The obtained multilayer ceramic capacitor was evaluated as follows. Here, the evaluation of the temperature characteristics of the relative permittivity, dielectric loss, and capacitance was all 10 samples, and the average value was obtained.
(1) Relative permittivity The capacitance is measured under the measurement conditions of a temperature of 25 ° C., a frequency of 1.0 kHz, and a measurement voltage of 1 Vrms. From the obtained capacitance, the thickness of the dielectric layer and the effectiveness of all layers of the internal electrode layer are measured. It was calculated based on the sum of areas and the dielectric constant of vacuum.
(2) Dielectric loss It measured on the same conditions as an electrostatic capacitance.
(3) Temperature characteristics of relative permittivity The capacitance was measured at a temperature of 125 ° C., and the rate of change relative to the capacitance at 25 ° C. was determined. In addition, by applying a DC voltage of 25 V, the capacitance at 125 ° C. was measured, and the rate of change with respect to the capacitance at 25 ° C. in a no-load (DC = 0 V) state was obtained (hereinafter referred to as high temperature load). This is called the temperature change rate of the relative permittivity in the state.
(4) High-temperature load test The test was performed at a temperature of 170 ° C. under an applied voltage of 170V. The number of samples in the high-temperature load test was 30 samples, and the average failure time, which was the time when the failure probability reached 50%, was examined. (5) Measurement of rare earth element (RE) concentration, concentration gradient and crystal particle ratio (b / (a + b)) in crystal grains and average particle diameter of crystal grains Concentration distribution of rare earth elements (RE) in crystal grains After polishing the dielectric ceramic cross section, draw a circle containing about 30 crystal grains on the image displayed on the monitor attached to the transmission electron microscope, and select the crystal grains that fall within and around the circle. Then, elemental analysis was performed using a transmission electron microscope equipped with elemental analysis equipment. In this embodiment, a unit area is a circle containing about 30 crystal grains. The crystal particles to be selected at this time are obtained by calculating the area of each particle by image processing from the outline, and calculating the diameter when replaced with a circle having the same area, and the calculated crystal particle diameter is approximately 0.08 to 0. Crystal grains in the range of .60. The spot size of the electron beam at the time of analysis was 0.5 to 2 nm, and the location to be analyzed was a position 20 nm (± 1 nm) deep from the grain boundary of the crystal grains. Specifically, when the concentration of the rare earth element (RE) in the crystal grain is obtained, an electron beam is applied to the center of the crystal grain, and the main element contained in the crystal grain (barium (Ba) (Ba) ), Titanium (Ti), vanadium (V), magnesium (Mg), manganese (Mn) and rare earth element (RE)) were determined as 100 atomic%, and the ratio of rare earth element (RE) was determined from this amount. .

  Next, when determining the concentration gradient of the rare earth element (RE), the location to be analyzed is in the range from the vicinity of the grain boundary of the crystal grains to the center position of the central portion, and is almost equal on the straight line drawn toward the center. The points were located at intervals, and were determined from values analyzed in the vicinity of the grain boundary and at a depth of approximately 20 nm and 200 nm from the grain boundary. In this case, the value obtained by subtracting the rare earth element (RE) concentration at a depth of 19 to 21 nm and 195 to 205 nm from the concentration of the rare earth element (RE) at the grain boundary (0 to 1 nm) of the crystal grain (concentration of the rare earth element). Was divided by the distance of the analyzed range (for example, 20 nm-0 nm = 20 nm, 200 nm-0 nm = 200 nm) to obtain a concentration gradient. Thereafter, the crystal grain 9a of the first crystal group and the crystal grain 9b of the second crystal group were determined by determining the concentration gradient of the rare earth element (RE) for each crystal particle. This analysis was performed at five locations for each sample to determine the average value.

In such an analysis, a crystal particle having a rare earth element (RE) concentration gradient of 0.05 to 0.20 atomic% is referred to as “crystal particle constituting the first crystal group”, and the rare earth element (RE) A crystal grain having a concentration gradient of 0.03 atomic% or less was designated as “crystal grain constituting the second crystal group”.

  Regarding the concentration of calcium in the crystal particles, elemental analysis was performed on the crystal particles present on the polished surface obtained by polishing the cross section of the dielectric ceramic using a transmission electron microscope provided with an elemental analysis device. At this time, the spot size of the electron beam is 3 nm or less, the center part of the crystal particles is analyzed, and the total amount of Ba, Ti, Ca, V, Mg, Y, RE (rare earth element) and Mn detected by the analysis is 100%. The ratio of calcium was determined. As a result, it was confirmed that calcium was contained at a ratio shown in Table 1. The crystal particles to be analyzed were selected by drawing a circle with about 10 crystal particles in the approximate center shown in the microscope observation monitor (photo). The center part of the crystal grains was the center of a circle drawn along the outline of each crystal grain.

  The average particle diameter of each of the crystal grains constituting the first crystal group and the crystal grains constituting the second crystal group is measured with a transmission electron microscope on the polished surface obtained by polishing (ion milling) the cross section of the dielectric ceramic. The projected image is taken into a computer, the contours of the crystal particles present on the image are processed, the area of each particle is obtained, and the diameter when replaced with a circle with the same area is calculated and calculated. It calculated | required from the average value of 30 crystal grains. In this case, the crystal particle 9a and the crystal particle 9b are distinguished from each other based on the result of the concentration gradient of the rare earth element (RE) previously obtained from the crystal particles, and the average value is obtained for each to obtain the average particle size of the crystal particles. It was.

In the dielectric ceramic, the area ratio of the crystal grains constituting the second crystal group to the total area of the crystal grains constituting the first crystal group and the crystal grains constituting the second crystal group, b / (a + b) (Where a represents the area of the crystal grains 9a constituting the first crystal group, and b represents the area of the crystal grains 9b constituting the second crystal group). It calculated from the data which calculated | required the average particle diameter of 9b. The b / (a + b) ratio of the prepared sample was equivalent to the mixing ratio of the raw material powder and the coating powder.
(6) Composition analysis of sample The composition analysis of the sample which is the obtained sintered compact was performed by ICP analysis and atomic absorption analysis. In this case, the obtained dielectric porcelain mixed with boric acid and sodium carbonate and dissolved in hydrochloric acid is first subjected to qualitative analysis of the elements contained in the dielectric porcelain by atomic absorption spectrometry, and then specified. The diluted standard solution for each element was used as a standard sample and quantified by ICP emission spectroscopic analysis. Further, the amount of oxygen was determined using the valence of each element as the valence shown in the periodic table. Manganese was determined in terms of MnO. As a result of the analysis, the composition of the dielectric layer was consistent with the prepared composition for all the samples. Tables 1 to 6 show the results of the composition and properties.
It was shown to. Sample No. Reference numerals 38, 39, 95 and 96 are reference samples.

  As is apparent from the results of Tables 1 to 6, sample No. 1 to 35, 38 to 92, and 95 to 120, a DC voltage of about 25 V is applied at 125 ° C. with reference to the capacitance measured under the condition that no DC voltage is applied at room temperature (25 ° C.). The change rate of the electrostatic capacity when it was done was within 73%.

  Sample No. 1-3, 6, 7, 10, 13, 14, 17, 19, 20, 23, 24, 27, 28, 31-35, 40, 42-47, 50, 51, 54-63, 64, 65, 68, 69, 72, 75, 76, 79, 81, 82, 85, 86, 89, 90, 97, 99 to 104, 107, 108 and 111 to 120, the ratio of the dielectric ceramic at room temperature (25 ° C.) The dielectric constant is 2000 or more, the temperature characteristic of the dielectric constant is −13.8% or less, and the relative dielectric constant measured in a state where no DC voltage is loaded at 25 ° C. (no load state), The rate of change of relative permittivity measured with a DC voltage of 25 V applied to the dielectric layer at 125 ° C. can be made within −51.8% (in the direction approaching NPO (± 0%)). 170V DC voltage is evaluated under application conditions. High temperature load lifetime is is equal to or greater than 34 hours.

  Among them, the content of manganese contained in the dielectric ceramic is 0.30 to 0.50 mol in terms of MnO, and the ratio of the second crystal particles to the first and second crystal particles (b / Sample No. (a + b)) of 0.4 to 0.6. 1-3, 6, 7, 10, 13, 14, 17, 19, 20, 23, 24, 28, 31-35, 40, 42, 43, 45-47, 50, 51, 54-63, 64, 65, 68, 69, 72, 75, 76, 79, 81, 82, 85, 86, 90, 97, 99, 100, 102-104, 107, 108 and 111-118 The rate of change in relative permittivity measured with a DC voltage of 25 V applied was within -51.5%.

  Furthermore, sample No. 1 in which the concentration of calcium contained in the crystal particles was 0.1 to 9 mol%. 1-3, 6, 7, 10, 13, 14, 17, 19, 20, 23, 24, 28, 31-35, 40, 42, 43, 45-47, 50, 51, 54-56, 58- 63, 64, 65, 68, 69, 72, 75, 76, 79, 81, 82, 85, 86, 90, 97, 99, 100, 102-104, 107, 108 and 111-113, and 115-120 Then, the dielectric loss was 3.6% or less.

  Among them, the crystal grains are classified into a first crystal particle having a calcium concentration of less than 0.3 atomic% and a second crystal having a calcium concentration of 0.3 atomic% or more in the crystal particle. Sample no. 1-3, 6, 7, 10, 13, 14, 17, 19, 20, 23, 24, 28, 31-35, 40, 42, 43, 45-47, 50, 51, 54-56, 58- 61, 64, 65, 68, 69, 72, 75, 76, 79, 81, 82, 85, 86, 90, 97, 99, 100, 102-104, 107, 108 and 111-113, 115-118 The dielectric loss was 3.5% or less, and the temperature change rate of the relative dielectric constant under the condition where no DC voltage was applied was 13.7% or less.

  Further, when the crystal particles constituting the dielectric ceramic did not contain calcium or the like (calcium concentration in the crystal particles was less than 0.1 atomic%), the dielectric loss (dielectric loss tangent) was less than 2%.

  Furthermore, samples (sample Nos. 34, 64, 65, 68, 69, 72, 75, 76, 79, 81, 82, 85, in which the rare earth element (RE) contained in the dielectric ceramic is gadolinium (Gd). 86, 89, 90, 97, 99-104, 107, 108, and 111-120) are not compared to samples of the same composition using other rare earth elements (Tb, Dy, Ho, Er, Yb). The temperature change rate of the relative permittivity in the load state and the high temperature load state was small, and the relative permittivity and the high temperature load life at room temperature (25 ° C.) were high.

  In contrast, sample no. 36, 37, 93, and 94, measured at 25 ° C. with a DC voltage of 25 V applied to the dielectric layer at a relative dielectric constant measured at 25 ° C. with no DC voltage applied (no load state). The relative dielectric constant change rate was greater than −73%.

DESCRIPTION OF SYMBOLS 1 ...... Capacitor body 3 ... External electrode 5 ... Dielectric layer 7 ... Internal electrode layer 11 ... Grain boundary phase 9 ... Crystal grain 9a ... 1st The crystal particles 9b constituting the crystal group of the crystal grains constituting the second crystal group

Claims (7)

A dielectric layer comprising a dielectric porcelain containing crystal grains mainly composed of barium titanate and containing at least one rare earth element (RE) selected from the group of terbium, dysprosium, holmium, erbium and gadolinium. cage, wherein the crystal grains, at the position of depth 20nm from the grain boundary, and crystal particle concentration of the first crystal group which is 0 to 0.5 atomic% of the rare earth element (RE), said first crystal group high concentration of the rare earth element (RE) than the crystal grains, and a crystal grain of the second crystal group concentration is a 0.3-0.9 atomic%, the crystal grains of the first crystal group the difference is 0.1 atomic% to 0.7 atomic% der following concentrations of the rare earth element (RE) and the second crystal group of crystal grains and is, crystal grains of the second crystalline group the first Average grain size than crystal grains Capacitor characterized by large . The dielectric ceramic contains vanadium, magnesium, manganese, and yttrium, and 100 moles of titanium constituting the barium titanate,
The vanadium is 0.05 to 0.20 mol in terms of V ₂ O ₅ ,
The yttrium is 0.5 to 2.0 mol in terms of Y ₂ O ₃ ,
The magnesium is 1.0 to 3.0 mol in terms of MgO,
The manganese is 0.22 to 0.50 mol in terms of MnO,
The rare earth element (RE) is 0.65 to 2.80 mol in terms of RE ₂ O ₃ ,
The concentration of the rare earth element (RE) at a position 20 nm deep from the grain boundary of the crystal grains of the first crystal group is 0.02 to 0.42 atomic%,
The concentration of the rare earth element (RE) at a position 20 nm deep from the grain boundary of the crystal grains of the second crystal group is 0.45 to 0.70 atomic%;
The average particle diameter of the crystal particles constituting the first binding Akiragun is 0.10～0.18Myuemu, with an average grain size of crystal grains constituting the second binding Akiragun is 0.2~0.5μm ,
When the area of the crystal grains constituting the first crystal group and the area of the crystal grains constituting the second crystal group, which are found per unit area of the polished surface of the dielectric ceramic, are b, , B / (a + b) is 0.4 to 0.7.   The capacitor according to claim 2, wherein the manganese is 0.30 to 0.50 mol in terms of MnO, and the b / (a + b) is 0.4 to 0.6. The crystal particles contain calcium, the first crystal particles in which the concentration of calcium in the crystal particles is less than 0.3 atomic%, and the concentration of calcium in the crystal particles is 0.3 atomic% or more. The capacitor according to claim 1, wherein the capacitor is a composite particle having two crystal particles.   5. The capacitor according to claim 4, wherein the concentration of the calcium contained in the second crystal particles is 0.1 to 9 mol%.   4. The capacitor according to claim 1, wherein the crystal particles are crystal particles of barium titanate.   The capacitor according to claim 1, wherein the rare earth element (RE) is the gadolinium.