TW201007788A - Laminated ceramic capacitor - Google Patents

Abstract

Disclosed is a laminated ceramic capacitor comprising a dielectric ceramic that is composed mainly of barium titanate and contains vanadium, magnesium, manganese, rare earth elements stated in the description, and terbium in respective proportions specified in the description. The crystal constituting the dielectric ceramic comprises a first group of crystals formed of first crystal grains having a calcium concentration of not more than 0.2 atomic% and a second group of crystals formed of second crystal grains having a calcium concentration of not less than 0.4 atomic%. The dielectric ceramic satisfies a requirement of C2/(C1 + C2) of 0.3 to 0.7 wherein C1 represents the area of the first crystal grains that appear on a polished surface of the dielectric ceramic; and C2 represents the area of the second crystal grains that appear on the polished surface of the dielectric ceramic. In an X-ray diffraction chart for the dielectric ceramic, the diffraction intensity of (200) plane attributable to cubic barium titanate is larger than the diffraction intensity of (002) plane attributable to tetragonal barium titanate. The Curie temperature is 95 to 105 DEG C.

Description

201007788 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a type of recording layer which is composed of a rabbit capacitor having a different calcium concentration, in particular, a dielectric layer ceramic capacitor. The small and high-capacitance product of the 鈇 鈇 鈇 【 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前Frequency, the requirements for the ride are getting higher and higher. Therefore, a small-sized, high-capacitance layer of a multilayer ceramic capacitor is required to be thinned and high: a dielectric material constituting a laminated capacitor is formed as a layer 2 layer. The dielectric material of the dielectric layer of the capacitor has been used for the dielectric material that contains the acid-deficient yttrium as the main component (· 枓. In recent years, 'in the past, (four) _ powder and make _ dissolved in Qin The composite medium dielectric material in which the powder in the acid lock is mixed and used to make the dielectric brittle coexist is turned over in the laminate_capacitor (for example, refer to Patent Document D. The use of the above-mentioned barium titanate powder and solid solution of calcium In the dielectric ceramic produced by the powder in the barium titanate, each of the oxides of magnesium, rare earth elements and manganese is used as an additive. Then, when calcined, the additives are solid-dissolved in the barium titanate powder and the calcium is solidified. It is dissolved in the vicinity of the surface of each of the powders in the barium titanate to form a crystal grain having a so-called core-shell structure to improve the dielectric constant and the dielectric property of the dielectric constant, etc. 098109473 3 201007788 Here, the crystal grain The core-shell structure refers to a structure in which a core portion which is a central portion of a crystal grain and a shell which is physically and chemically different from a shell portion which is an outer shell portion. Occupied by the crystal phase of tetragonal crystal The state in which the shell portion is occupied by the crystal phase of the cubic crystal. The dielectric constant of the multilayer ceramic capacitor in which the dielectric ceramic composed of the crystal grains of the core-shell structure is used as the dielectric layer is improved, and the dielectric constant is The temperature characteristic satisfies X7R (the temperature change rate of the dielectric constant at 25 ° C is within ±15% from -55 to 125 ° C.) In addition, the change in dielectric constant when the applied AC voltage is increased by ❹ However, in the above-mentioned laminated ceramic capacitor, if the thickness of the dielectric layer is thinned to, for example, about 2, there is a problem that the life characteristics in the high-temperature load test are largely lowered. [Patent Document 1] JP-A-2001-156450 SUMMARY OF INVENTION Technical Problem The object of the present invention is to provide a laminated ceramic capacitor having a dielectric layer which is high dielectric. The coefficient and the stability of the dielectric property of the dielectric constant are excellent, and the increase in the dielectric constant when the AC voltage is increased is better than J, and the life characteristics of the horse temperature load test are excellent. (Means for solving the problem) The multilayer ceramic capacitor of the Ming is formed by alternately laminating a dielectric layer and an internal electrode layer to form 'the dielectric layer is composed of barium titanate as a main component, and contains calcium, magnesium, vanadium, manganese and strontium at 09473 4 201007788 and A dielectric ceramic of at least one rare earth element selected from the group consisting of ruthenium, pin, chin, and slant. The dielectric ceramics are contained in a V 2 〇 5 ratio with respect to 100 mils of titanium strontium strontium silicate. The above-mentioned vanadium is 0.02 to 0.2 mol, and the above-mentioned magnesium in the range of Mn 2 to 〇8 mol is 〇.1 to 0.5 mol of the above manganese, and the re203 conversion juice is 0.3. At least one of the above-mentioned rare earth elements selected from the group consisting of 〇 8 8 莫 、 、 、 钢 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼 轼The crystal constituting the dielectric ceramics has a 帛1 crystal group composed of the first crystal grains having the barium titanate as a main component and the calcium concentration of 〇2 atom% or less; The 2 crystal group is composed of the second crystal grain having the barium titanate as a main component and the calcium concentration of 〇4 atom% or more. When the area of the first crystal grain observed on the polished surface of the dielectric ceramic is C1 and the area of the second crystal grain is C2, C2/(C1 + C2) is 0.3~ 0.7. In the X-ray diffraction pattern of the above dielectric ceramic, the diffraction intensity of the (fine) face of the cubic crystal of barium titanate is larger than the diffraction intensity of the (〇〇2) face of the barium titanate exhibiting tetragonal. Curie temperature is 95~1〇5. (^. % Further, the above rare earth element is not RE, which is based on the Rare earth of the rare earth element in the periodic table. (Effect of the invention) According to the present invention, the following dielectric layer can be obtained. A multilayer ceramic capacitor having a high dielectric constant and a decrease in the dielectric constant temperature variation 098109473 5 201007788, and a small increase in the dielectric constant when the applied AC voltage is increased (dielectric The AC voltage dependence of the constant is small, and the lifetime is excellent in the high-temperature load test. [Embodiment] The multilayer ceramic capacitor of the present invention will be described in detail based on the circle 1 and FIG. 2. As shown in FIG. The multilayer ceramic capacitor is formed with external electrodes 3 at both end portions of the capacitor body 1. The external electrode 3 is formed by firing an alloy paste of Cu or Cu and Νι, for example, and the capacitor body 1 is made of dielectric ceramic. The dielectric layer 5 and the internal electrode layer 7 are alternately laminated. In Fig. 1, the state of the dielectric layer 5 and the internal electrode layer 7 is simplified, and the dielectric layer of the ceramic capacitor of the present invention is dielectric. 5 and the internal electrode layer 7 even up to several hundred layers of the laminate. 9 :: The second dielectric layer 5 composed of dielectric ceramics is composed of the crystal grains 9 and the boundary phase U. The thickness of the dielectric layer 5 is particularly preferably 1 to below. By means of the small size and high capacitance of the container, the laminated layer can be electrically charged, and the dielectric layer can be reduced. The thickness of 5 is ... Stabilized. It is not uniform and can make the temperature characteristics of the capacitor as the material for forming the internal electrode layer 7 as a result of the suppression of the material, and even if the layer is high, the layer can be especially high. The dielectric layer 5 in the present invention is preferably a Ni or the like, and is preferably Ni. The aspect of simultaneous calcination is 1 098109473 201007788 The dielectric of the dielectric layer 5 constituting the multilayer ceramic capacitor of the present invention. The ceramics consists of barium titanate as the main component and contains calcium (Ca), magnesium (Mg), vanadium (V), 猛 ()η) and 轼 (Tb), and Zi (Y), 镝 (Dy), A sintered body of at least one rare earth element (RE) selected from the group consisting of Ho (Ho) and 铒 (Er). The above sintered body is 'relative to the titanium constituting barium titanate〗 〇〇莫耳, containing V.〇2~〇·2 Moer's hunger in terms of V2〇5, in terms of MgO, 0.2 to 0.8 moles of magnesium, in terms of MnO, 〇.1~〇. 5 Molybdenum manganese, at least one rare earth element selected from the group consisting of: 0.3 to 0.8 moles of self-reported, pin, tantalum and steel, and converted to Tb407 as 〇.〇2~ Further, the crystal grains 9 formed in the dielectric ceramic are composed of a first crystal grain 9a and a second crystal grain 9b, and the first crystal grain 9a is composed of barium titanate as a main component. An i-th crystal group composed of crystal grains having a calcium concentration of 0.2 atom% or less, and the second crystal grain 9b is composed of a crystal grain having a barium titanate as a main component and having a calcium concentration of 0.4 atom% or more. The second crystal group composed. A grain boundary phase 11 is formed between the crystal grains 9, 9. The main component of the grain boundary phase u is a glass component, and partially contains the above-mentioned subcomponents such as magnesium, vanadium, manganese, cerium, and rare earth elements contained in the dielectric ceramic. In the dielectric ceramic, the ratio of the first crystal grains 9a to the second crystal grains 9b is such that the area of the first crystal grains 9a observed on the polished surface of the dielectric ceramic is Cl. When the area of the second crystal grain 9b is C2, C2/(C1 + C2) is 0.3 to 0.7. 098109473 7 201007788 Furthermore, in the x-ray diffraction pattern of the above dielectric ceramic, it is shown that the diffraction intensity of the (200) plane of the cubic crystal of barium titanate is larger than that of the (002) plane of the barium titanate exhibiting tetragonal crystal The intensity of the shot is, and the Curie temperature is 95~1〇5. Hey.

The dielectric ceramic of the present invention having such a specific configuration has a dielectric constant of room temperature (MC) of 3,500 or more, a dielectric loss of 125% or less, and a temperature characteristic of a dielectric constant satisfying X6S (ie, The temperature change rate of the dielectric constant based on 25 is _55 to 1 〇 rc is within 22% of the soil, and hereinafter sometimes referred to as "X6S". In addition, the dielectric constant of the dielectric ceramic when the Ac voltage is ν is 2 or less of the dielectric constant when the AC voltage is 〇.〇1 v. Further, the dielectric ceramic is subjected to a high-temperature load test (temperature · 1 〇 5 it, electric wish: h5 times the rated voltage, test time: 1 〇〇〇 or less sometimes referred to as "high temperature load test") The occurrence is suppressed. Therefore, the laminated ceramic capacitor of the present invention having the dielectric layer 5 composed of the dielectric material has high reliability. The reason for this will be described in detail below. In place of the titanium (10) moth which constitutes (4) niobium, if the content of niobium is v2〇5, one to G.G2 moir, the reliability in the high temperature load test decreases. On the other hand, if the content of hunger is more than 〇2 mol in terms of v2〇5, the dielectric constant at room temperature becomes low. Calculation::·20%::钡:^ WO莫耳 If the content of magnesium is 岣. The temperature characteristic of the dielectric constant of the exchange + side m ′ is easily largely biased to the X6S condition as the temperature characteristic of the electrostatic capacitance. Another 098109473 201007788 At 0.8 m, the dielectric constant at room temperature changes, on the one hand, if the content of magnesium is low, 0 constitutes the titanium barium titanate, if the content of the clock is changed to G.1 In the case of Mohr, the insulation resistance of the dielectric layer 5 is lowered, so that the reliability in the high-loading is lowered. On the other hand, if the content of the fierce content is in the case of G.5 Moer, the dielectric constant at room temperature becomes lower. (4) In the case of titanium (10) Mo, which constitutes titanium, if the content of at least one rare earth element selected from Ziji, _, 鈥, and oblique @ is less than Μ莫耳 in terms of RE2〇3, it is reliable in high temperature load test. Sexual decline. On the other hand, if the content of the above rare earth element is more than 〇 8 mol in terms of RE2 〇 3, the dielectric constant at room temperature becomes low. Compared with the titanium 100 mil which constitutes barium titanate, if the content of strontium is less than 0.02 mol in terms of Tb4〇7, the solid of vanadium, magnesium, and rare earth elements in barium titanate as a main component The amount of solution is reduced. Therefore, the Curie phase of the dielectric ceramics is at the Curie temperature (about 125 °C) of the acid-free pot, and the reliability under the high-temperature load test is lowered. On the other hand, if the amount of 铽Tb4〇7 is more than 0.2 mol, the amount of solid solution of vanadium, magnesium, manganese, and rare earth elements in barium titanate as a main component increases. Therefore, compared with the dielectric constant when the AC voltage is set to 0.01 v, the dielectric constant increases when the Ac voltage is 丄V (the AC voltage dependence of the dielectric constant is large), and the rated power changes repeatedly. The change in the electrostatic capacitance of the dielectric ceramic becomes large. The composition of the preferred dielectric ceramics is preferably 0.02 to 0.08 moles of vanadium in the form of V205, which is 0.3 to 0.6 in terms of MgO, for the composition of 100 mils of titanium 098109473 9 201007788. Molybdenum magnesium, which is 0.2 to 0.4 mol of manganese in terms of MnO, and is at least one rare earth element selected from the group consisting of 〜, 镝, 鈥, and bait in terms of RE203, and converted to Tb407. Calculated as 0.02~0.08 moles. The dielectric ceramics having the composition can increase the dielectric constant at room temperature to 3700 or more, and the dielectric constant when the AC voltage is 1 V can be set to be 0.01 V when the AC voltage is set to 0.01 V. The electrical constant is 1.5 times or less. Further, as the rare earth element, a higher dielectric constant and a higher insulation resistance are preferable. Further, the dielectric ceramic is preferably contained in an amount of 0.05 to 0.08 mol in terms of Tb407 with respect to 100 mol of titanium constituting barium titanate. Thereby, the coefficient of variation (σ/χ, σ: standard deviation, X: average value) of the dielectric constant of the dielectric ceramic can be reduced. Therefore, in the case of manufacturing a multilayer ceramic capacitor, even if there is a difference in the calcination temperature, a laminated ceramic capacitor having a small uneven capacitance can be obtained. Further, as described above, in the dielectric ceramic, the ratio of the first crystal grains 9a to the second crystal grains 9b is such that the first crystal grains 9a are observed on the polished surface of the dielectric ceramic. When the area is C1 and the area of the second crystal grain 9b is C2, C2/(C1 + C2) is 0.3 to 0.7. That is, when C2/(C1 + C2) is less than 0.3, the ratio of the second crystal grains 9b containing Ca is small, and the dielectric constant at room temperature is lowered. On the other hand, if 098109473 10 201007788 C2/(C1 + C2) is more than 〇.7, the dielectric constant at room temperature increases, but the life in the high-temperature load test decreases. C2/(C1 + C2) is particularly desirable & G4 to G6. If it is in this range, the dielectric constant of the dielectric ceramic at room temperature can be increased to 40 Å or more. Further, the calcium concentration of the second crystal grains 9b is particularly preferably 0.5 to 2.5 atom%. If the ship's degree is within this range, it can be fully dissolved in the titanic acid. Further, since the amount of calcium compound which remains undissolved in the grain boundary or the like is reduced, the dielectric constant of the dielectric constant is increased, so that a high dielectric constant can be achieved. Further, the first crystal grains 9a include those having a calcium concentration of zero. In addition, the Curie temperature in the present invention means a range in which the temperature characteristic of the dielectric constant is measured (the temperature at which the dielectric constant of 6 〇 15 (rc) reaches the maximum. The calcium concentration in the crystal grain 9 is attached. A transmission electron microscope of an elemental analysis apparatus performs elemental analysis on the crystal grains 9 present on the polishing surface until the cross section of the dielectric layer 5 is polished by ion milling to the extent that it can be observed. The spot size of the beam is set to 5 nm, and the analysis portion is set at a substantially equal interval from the grain boundary in the straight line drawn from the vicinity of the grain boundary of the crystal grain 9 to 4 points. The ratio of the total amount of Ba, Ti, Ca, V, Mg, RE (rare earth element) and Μη detected by the point is set to 1〇〇〇/〇, and the calcium determined at each measurement point is obtained. The average value of the ratio is taken as the calcium concentration. Then, the crystal grains having a calcium concentration of 0.2 atom% or less are used as the first crystal grains 9a, and the obtained crystals having a calcium concentration of 0.4 atom% or more and 098109473 11 201007788 are obtained. The grain is the second crystal grain %. The crystal grain 9 of the calcium concentration is determined as First, a photograph of the polished surface obtained by grinding the cross section of the dielectric layer 5 constituting the laminated ceramic capacitor (magnification: 20,000 to 100,000 times) is taken using a transmission electron microscope. Then, in the photograph A circle enclosing 30 crystal grains 9 is drawn thereon, and the area of each particle is obtained by image processing based on the contours of the respective crystal grains 9 located in the circle and the circumference, and the diameter when replacing the circle having the same area is calculated. Then, the diameter of the obtained crystal grain 9 is within a range of ±30% of the average particle diameter determined by the method described later as the crystal grain 9. Further, each of the inside and the circumference of the circle is obtained. The total area of each of the first crystal grains 9a and the second crystal grains 9b selected and measured in the crystal grains 9 is obtained as a value of C2/(C1 + C2). Further, the center of the crystal grains 9 is the crystal grains 9 The center of the circle is inscribed, and the vicinity of the grain boundary of the grain 9 means a region from the grain boundary of the grain 9 to the inner side of 5 nm. Moreover, the inscribed circle of the grain 9 will be worn by The image reflected by the transmission electron microscope is taken into the computer and the grain 9 is drawn on the surface of the lens. In the circumstance of the circle, the center of the crystal grain 9 is determined. Fig. 3 is an X-ray diffraction pattern of a dielectric ceramic constituting the multilayer ceramic capacitor of the sample No. 3 in the later-described embodiment, which constitutes the multilayer ceramic capacitor of the present invention. The dielectric ceramic has a diffraction pattern as shown in the X-ray diffraction pattern of Fig. 3. Fig. 4 is a graph showing the temperature characteristics of the electrostatic capacitance of the multilayer ceramic capacitor of sample No. 3. The multilayer ceramic capacitor of the present invention. With 098109473 12 201007788 there is a temperature characteristic of the electrostatic capacitance shown in Fig. 4. In the X-ray diffraction diagram of Fig. 3, the (2〇〇) plane of the cubic crystal barium titanate (26> = 45.3. The χ-ray diffraction peaks of the (〇〇2) plane of the tetragonal barium titanate (near 20 = 45.1°) are overlapped to form a broad diffraction peak. Further, the diffraction intensity (Ic) of the (2 Å) plane showing the cubic crystal of barium titanate is larger than the diffraction intensity (It) of the (002) plane showing the tetragonal barium titanate. The crystal structure is similar to the conventional X-ray diffraction pattern of the core-shell structure, but as shown in Fig. 4, the Curie temperature (Tc) of the dielectric ceramic constituting the multilayer ceramic capacitor of the present invention is 95 to 1 〇 5 ° C ' differs from the dielectric properties of a conventional dielectric ceramic having a core-shell structure with a Curie temperature of i25 ° C. That is, a dielectric ceramic having a core-shell structure obtained by solid-solving an additive component such as magnesium, manganese, and a rare earth element into a bismuth silicate as a main component shows a Curie temperature of pure barium titanate (125. The Curie temperature in the vicinity of the crucible. In contrast, the dielectric ceramic constituting the dielectric layer 5 of the multilayer ceramic capacitor of the present invention is as described above, and is dissolved in calcium barium, vanadium, and magnesium in barium titanate. , manganese, and at least one rare earth element selected from lanthanum, cerium, lanthanum and cerium, and lanthanum. Therefore, despite the diffraction of the (2 〇〇) plane of the barium titanate which shows cubic crystal in the X-ray diffraction pattern The crystal structure having a strength greater than the diffraction intensity of the (〇〇2) plane of the tetragonal barium titanate, but having a Curie temperature of 95 to 1 〇 5 ° C and having a property of being biased toward the room temperature side is generally considered to be In addition to the addition of components such as vanadium, magnesium, manganese, and rare earth elements, a small amount of cerium is solid-dissolved, whereby the added component diffuses in a specific state inside the dielectric ceramic, so that the Curie temperature can be 95 to 105. 098109473 13 201007788 For example, in the laminated ceramic capacitor constituting the present invention In the dielectric ceramic of the device, the concentration difference between the first crystal grain 9 a and the second crystal grain 9 b in the surface layer portion minus the manganese concentration at a depth of 1 〇 nm is 〇 3 atom%. In the following, the concentration difference of the rare earth element concentration in the surface layer portion minus the rare earth element concentration at a depth of 1 〇 nm is atomic % or more. Specifically, as shown in Figs. 5(a) to 5(c). 5(a) is a graph showing a change in concentration of rare earth elements and manganese contained in crystal grains of a dielectric ceramic constituting the multilayer ceramic capacitor of the sample N〇3 in the later-described embodiment. The dielectric ceramic is the present invention. Fig. 5(b) is a graph showing changes in the concentration of rare earth elements and manganese contained in crystal grains of a dielectric ceramic constituting the multilayer ceramic capacitor of the sample N〇1 in the later-described embodiment. The electroceramic ceramic is obtained by solid-solving such an additive component of magnesium, manganese, and a rare earth element in barium titanate as a main component, and has a core-shell structure having a Curie temperature of 125. (: Fig. 5(c) A crystal grain of a dielectric ceramic constituting a multilayer ceramic capacitor of the sample N〇6 in the later-described embodiment A graph showing changes in the concentration of rare earth elements and manganese contained in the medium. The dielectric_money is obtained by adding magnesium, manganese, and a rare earth element to a barium titanate as a main component and adding a ruthenium in excess. Further, in ϋ 5 (a) to (c), the rare earth element is yttrium (7). In Fig. 5 (a), the rare earth element (γ) shows a large concentration change near the surface of the crystal grain 9 'relative to this The concentration of manganese (Μη) in the vicinity of the surface changes little. 098109473 201007788 On the other hand, in Figure 5(b), the two components of rare earth element (Y) and manganese (Μη) are displayed near the surface of the crystal grain 9. The concentration of the large concentration changes. In Fig. 5(c), the concentrations of the rare earth element (Υ) and manganese (Μη) in the vicinity of the surface of the crystal grain 9 are small. As described above, the multilayer ceramic capacitor of the present invention has a large change in the concentration of the rare earth element (Υ) in the vicinity of the surface of the crystal grain 9 constituting the dielectric ceramic, and the change in the concentration of manganese (Μη) is small. There is an intermediate structure between sample No. 1 and sample No. 6 ❿. Therefore, even if the crystal structure is similar to the core-shell structure, the Curie temperature is also 95 to 105 °C. Therefore, in the multilayer ceramic capacitor of the present invention, the element of diffusion compensates for the oxygen deficiency in the crystal grain, whereby the dielectric properties of the dielectric ceramic are improved, and the life in the high temperature load test can be improved. In other words, when the amount of solid solution of manganese and rare earth elements in the crystal grains 9 is small, the proportion of the core portion containing defects such as a large number of oxygen vacancies increases. Therefore, it is considered that, in the case where a DC voltage is applied, the oxygen vacancies or the like inside the crystal grains 9 constituting the dielectric material are likely to be carriers for carrying charges, and the dielectric properties of the dielectric ceramics are lowered. Vanadium and money are added to the dielectric ceramic constituting the dielectric layer 5 in the laminated ceramic capacitor of the present invention, and the solid solution state of the rare earth element including the additive component of the above lanthanum and cerium is different. Thus, the Curie temperature is in the range of 95 to 105 °C. Therefore, it is generally considered that the carrier density of the oxygen vacancies or the like in the crystal grains 9 can be reduced by 'containing a large amount of rare earth elements and magnesium' and the oxygen vacancies inside the crystal grains 9 are made less, so that a higher insulation can be obtained. 098109473 15 201007788 The concentration of the rare earth element and manganese contained in the granule 9 was measured using a transmission electron microscope with an elemental analyzer (EDS).隹Use the sample of the coagulation to electrolyze the laminated ceramic by ion milling in the direction of the lamination; the knife is deposited to the extent that it can be observed, and the selected calcium concentration is selected on the ground dielectric layer. The measured first particles and second crystals 9b are measured. 9a

For each of the selected crystal grains 9a and 9b, the area of each particle is obtained from the contour by image processing, and the diameter when replacing the circle having the same area is calculated, and the respective crystal grains 9a and 9b are set to be at The first crystal grains 9a and the second crystal grains 9b in the range are selected from the crystal grains in the range of ±30% of the average particle diameter by the measurement method described later. The spot size of the electron beam when performing elemental analysis is set to 1 to 3 nm. another

The outer portion of the analysis portion is at least the surface layer portion of the crystal grain 9 and the depth from the surface layer portion at positions of 5 nm, 1 〇 nm, and 20 nm. Further, in the present invention, the surface layer portion of the crystal grain 9 means a region within 3 nm from the grain boundary of the cross section of the crystal grain 9. Then, the concentration of the rare earth element and the manganese in the surface layer portion of each of the crystal grains 9a and 9b is obtained for each of the first crystal grains 9a and the second crystal grains 9b, and a rare earth element having a depth of 1 nm from the surface layer portion is obtained. And the concentration of manganese. In Figs. 5(a) to 5(c), the position indicated by the arrow is a position at a depth of 10 nm from the surface layer portion. 098109473 16 201007788 Next, the respective crystal grains 9a and 9b are obtained from the rare earth elements at the position of the surface layer portion of each of the crystal grains 9a and 9b and the depth of the surface layer portion at a position of 1 〇 nm. The concentration of manganese in the surface layer portion minus the concentration of manganese at a depth of 1 〇 nm 2 and the concentration of rare earth elements in the surface layer portion of each of the crystal grains 9a and 9b minus the concentration of rare earth elements at a depth of 1 〇 nm And the concentration is poor. Specifically, this operation is performed for each of ten pairs of crystal grains, and the average value of the crystal grains 9 is calculated for a total of 20 values obtained from the respective crystal grains 9a and 9b. Further, although not shown, Magnesium, vanadium, and niobium are the same as manganese, and the concentration of each surface layer portion minus the concentration at a position where the depth is 1 〇 nm is 0.3 atom% or less. The composition of the multilayer ceramic capacitor constituting the present invention is In the dielectric ceramic of the electric layer 5, the average particle diameter of the crystal grains 9 including the first crystal grains 9a and the second crystal grains 9b is maintained only in terms of maintaining high dielectric constant and reducing dielectric loss. 'To be 0.1 / m or more, if you want to reduce the unevenness of the electrostatic capacitance, it can be set to 0.3 / zm or less, preferably 〇 14 ~ 〇 28 can be melon. If the grain 9 The average particle diameter is 〇14~〇28 " melon, and the following advantages are obtained: the dielectric constant is 3500 or more, the dielectric loss is 125% or less, the dielectric constant of the dielectric constant satisfies X6S, and the AC voltage is used. The dielectric constant at the time of v is equal to or less than 9 times the dielectric constant when the AC voltage is set to 〇.〇1 v, and satisfies the south temperature negative. Reliability in the test (no defect at 1〇5π, 1.5 times the rated voltage, 1000 hours or more) 098109473 17 201007788 For the average particle size of the grain 9, first, the capacitor body after the satin burning The fracture surface of the sample consisting of 1 was ground, and then a photograph of the internal tissue was taken using a scanning electron microscope (magnification: 2 〇〇〇〇 to 1 〇〇〇〇〇). Then, the image was drawn on the photo 2〇 ~3 〇 a circle of 9 grains, select the grains 9 in the circle and on the circumference. Then 'image the outline of each grain 9' to find the area of each particle, and calculate to replace it with the same area. The diameter of the circle is obtained, and the average particle diameter is obtained from the average value. On the other hand, in order to obtain the material capacitance H which can further improve the life characteristics in the high-temperature load test, it is another preferable composition as the dielectric material. Preferably, it is a hunger of 0.05 to 01 mol in terms of V2 相对 with respect to the titanium ruthenium constituting barium titanate, and is 〇2 to 〇8 mol of magnesium in terms of MgO. In terms of Mn〇, it is 〇·2~〇.3 Manganese, in terms of re2〇3, is at least 2 kinds of rare earth elements selected from 钇, 镝, 鈥, and 0.4 in terms of re2〇3, and 0.05 to 〇3 moles in terms of Tb4〇7, Preferably, the average grain size of the first crystal grain and the second crystal grain is 0.14 to 〇19, and the dielectric material having the composition and the average grain size of the crystal grain is obtained in a convenient condition. The temperature of the load test is increased to 125 1000 hours or more without any defective multilayer ceramic capacitor. Further, the dielectric ceramic of the present invention may contain a glass component as long as it maintains a desired range of properties. Improve the burning charge (sintering aid). ° help 098109473 18 201007788, and then the method of manufacturing the multilayer ceramic capacitor of the present invention will be described. First, it is expected to prepare a V205 powder with a powder of barium titanate powder (hereinafter referred to as = BT) and a powder of glutamic acid in the stearate (hereinafter referred to as private). MgO powder, and further prepared from Y2〇3 &, Dy2〇3 powder, H〇 powder and price powder, at least one type of su+> alizarin oxide powder and Tb407 powder and

MnC〇3 powder. P BCT powder is the IU solution of the substitution of A (four) - part (4) (four) as the main IU solution, which is represented by (β~-χ(4)τ. In this compound, Ca + in the Α position

The substitution amount of La is preferably x = 0.01 to 0.2. When the substitution amount of Ca is within this range, a crystal structure in which grain growth is suppressed can be formed by the coexistence structure with the first crystal grains 9a. Thereby, in the case where the obtained dielectric 陶曼 is used as a laminated ceramic capacitor, excellent temperature characteristics of the electrostatic capacitance can be obtained in the use temperature range. Further, Ca contained in V in the second crystal grains 9b is solid-dissolved in a state of being dispersed in the second crystal grains 9b. Further, the specific surface area of the BT powder and the BCT powder to be used is preferably 2 to 6 m 2 /g. If the specific surface area of the BT powder and the BCT powder is 2 to 6 m 2 /g, the first crystal grains 9 a and the second crystal are easily formed. The granule 9b maintains a crystal structure similar to that of the nucleus, and it is easy to dissolve the additive component in the crystal grains to bias the Curie temperature toward the low temperature side. In addition, the dielectric constant can be improved and the dielectric properties of the dielectric ceramic can be improved, thereby improving the reliability in the high temperature load test. 098109473 19 201007788 In addition, as for the additive, at least one rare earth element oxide powder, Tb4〇 powder, V2〇5 powder, MgO selected from the group consisting of 203 powder, Dy203 powder, Ho2〇3 taiwan and Εγ2〇3 powder. The powder and the MnC03 powder are preferably the same as the dielectric powder using the particle size (or specific surface area). Then 'relative to the total amount of BT powder and BCT powder 1 〇〇 mol, to 0.02 m of V2 〇 5 powder, 〇. 2 ~ 〇. 8 mol of MgO powder, 〇. 3 ~ 〇 · 8 m The rare earth element oxide powder, 0.1 to 0.5 mole of MnC〇3 powder, and 0.02 to 0.2 mole of Tb407 powder are used to adjust the raw material powder, and further, if necessary, to maintain the desired dielectric A range of characteristics is added as a glass powder of a sintering aid to obtain a raw material powder. When the total amount of the BT powder and the BCT powder as the main raw material powder is 1 part by mass, the amount of the glass frit powder added is preferably 0.5 to 2 parts by mass. Then, a special organic vehicle is added to the raw material powder to prepare a ceramic material. A sheet forming method such as a doctor blade forming method or a slit extrusion coating method is used to open a ceramic sheet. In this case, the thickness of the ceramic green sheet is preferably 0.5 to 3 am in terms of thinning and high insulation for realizing the capacitance of the dielectric layer 5 。. Thereafter, a rectangular internal electrode pattern was formed on the main surface of the obtained ceramic green sheet. The conductive paste to be the internal electrode pattern is preferably an alloy powder of Ni, Cu or the like. Then, 'the desired number of sheets of the ceramic green sheets in which the internal electrode patterns are formed are overlapped'. The upper and lower layers are the same number of sheets, and a plurality of ceramic green sheets having no internal 098109473 20 201007788 electrode patterns are formed thereon to form a sheet. Laminates. In this case, the internal electrode patterns in the sheet laminate are shifted by a half pattern in the longitudinal direction. Then, the obtained sheet laminated body was cut into a lattice shape, and the capacitor body molded body was formed so that the end portions of the internal electrode patterns were exposed. Such a lamination method can be formed by alternately exposing the end faces of the capacitor body molded body after the cutting by the internal electrode pattern. Then, the obtained capacitor body formed body is degreased and then calcined. The calcination temperature is preferably from 1100 to 1200X: for the purpose of controlling the solid solution of the additive in the BT powder and the BCT powder and the grain growth of the crystal grains. In order to obtain the dielectric ceramic of the present invention, BT powder and BCT powder having a specific surface area of 2 to 6 m 2 /g are used, and in each case, a predetermined amount of each of oxides of magnesium, chain, lanthanum and cerium is added as described above. Each of the oxide powders of at least one of the above rare earth elements selected from the group consisting of ruthenium, osmium, iridium and iridium is calcined at the above temperature as an additive. Thereby, the crystal grains obtained by using the BT powder and the BCT powder as main raw materials contain various additives, and the crystal structure which the crystal grains exhibit is similar to the structure of the core-shell structure, and the Curie temperature is lower than The well-known shows the circumference of the Curie temperature of the dielectric structure of the nuclear province. After calcination, the calcination is carried out by the method of making the Curie temperature lower than the Curie temperature of the dielectric core-shell structure of the conventional display, the first niobium 9a and the second crystal grain. The solid solution of the additive in 9b is improved, and as a result, a dielectric ceramic (10) 8109473 21 201007788 porcelain having high insulation and good life in a high temperature load test can be obtained. Further, in the present invention, in order to make the average grain size of the crystal grains 9 constituting the dielectric ceramic to be 0.19 or less, it is preferable to select a powder having a specific surface area of more than 5 m2/g. Further, after calcination, heat treatment was again performed in a weakly reducing atmosphere. This heat treatment is carried out in order to reoxidize the dielectric ceramic which is reduced during calcination in the reduction environment, and to restore the insulation resistance which is reduced by reduction during the calcination. In order to suppress further grain growth of the first crystal grains 9a and the second crystal grains 9b and increase the amount of reoxidation, the temperature of the heat treatment is preferably 9 〇〇 to u 〇 (rc. ❹ in the above manner A multilayer ceramic capacitor in which the i-th grain 9a and the second crystal grain are highly insulated and exhibits a Curie temperature of 95 to 105 C. Then, the opposite ends of the capacitor body i obtained by performing the above heat treatment are formed. The external electrode paste is applied and fired to form the external electrode 3. Further, a plating film may be formed on the surface of the external electrode 3 to improve mountability. The laminated capacitor of the present invention can be obtained in the above manner. The present invention will be described in detail with reference to the accompanying Examples. However, the present invention is not limited to the following examples. [Examples] <Production of laminated ceramic capacitors> First, as a raw material powder, Βτ powder and bct powder were prepared. (composition: xCax) Ti〇3, X = (10) 5), Mg 〇 powder, γ 2 〇 3 powder, d powder, η 〇 2 〇 3 powder, ΕΓ 2 〇 3 powder, Tb 4 〇 7 powder, squeezing powder, and V 2 〇 5 powder. 098109473 22 201007788 Then, the various powders were mixed at a ratio shown in Tables 1 to 3. In Tables 1 to 3, the blending ratios of the two powders are shown for the BT powder and the BCT powder. In addition, the ratio of the Mg powder, the Y2〇3 powder, the Dy2〇3 powder, the H0203 powder, the Er203 powder, the Tb407 powder, the MnC03 powder, and the v2〇5 powder is set to 100 mol per BT powder and BCT powder. The ratio. The purity of the raw material powders was 99.9%. The BT powder and the BCT powder were used in the sample Nos. 1 to 80, and the specific surface area was 4 m2/g, and the sample No. 81 and -11 were used in the sample No. 81 and -11 Å. MgO powder, γ2〇3 powder,

Dy2〇3 powder, Ηο2〇3 powder, Er203 powder, Tb407 powder, MnC03 powder, and νζ〇5 powder are used with an average particle diameter of 0.1. The sintering aid used was a glass powder composed of Si〇2 = 55, BaO = 20, CaO = 15, and Li20 = 1 〇 (mole %). The amount of the glass powder added is 1 part by mass based on 1 part by mass of the total amount of the barium powder and the BCT powder. Next, a mixed solvent of toluene and ethanol as a solvent was added using a cerium oxide ball having a diameter of 5 mm, and the raw material powders were wet-mixed. Then, the wet-mixed powder was placed together with a polyvinyl butyral resin in a mixed solvent of toluene and ethanol, and a ceramic slurry was prepared by wet-mixing using a cerium oxide ball having a diameter of 5 mm. Using this ceramic slurry, a ceramic green sheet having a thickness of 1.5 and 2.5 /zm was produced by a doctor blade forming method. Then, on the upper surface of the ceramic green sheets having thicknesses of 1.5 / zm and 2.5 / m, a plurality of rectangular internal electrode patterns containing Ni as a main component were formed. 098109473 23 201007788 The conductive paste for forming the internal electrode pattern is used by adding 15 parts by mass of BT powder to 1 part by mass of Ni powder having an average particle diameter of 0.3 /zm. Then, 200 pieces of ceramic green sheets printed with internal electrode patterns were laminated, and 20 pieces of ceramic green sheets having unprinted internal electrode patterns were laminated on the upper and lower surfaces thereof, and a press was used at a temperature of 60 ° C and a pressure of 1 Torr. 7 Pa, the time was 10 minutes, and the like, and a sheet laminate using a ceramic green sheet having a thickness of 1.5 // Γ m and a sheet using a ceramic green sheet having a thickness of 2.5 were produced. Laminates. Thereafter, each of the sheet laminates is cut into a predetermined size' to form a capacitor body molded body. Then, the capacitor body molded body was subjected to a debonding treatment in the air, and then calcined at 1,120 to 1,135 °C for 2 hours in a hydrogen-nitrogen gas to prepare a capacitor body. Further, the fabricated capacitor system was further subjected to reoxidation treatment at 1000 ° C for 4 hours in a nitrogen atmosphere. The size of the capacitor body is 0.95x0.48x0·48 mm3, the thickness of the dielectric layer is i or 2, and the effective area of the inner electrode layer of the ❹1 layer is 〇3 mm2. In addition, the "effective area" refers to an area of a portion where the internal electrode layers alternately formed in the lamination direction so as to be exposed on different end faces of the capacitor body, respectively. Thereafter, the calcined capacitor body was subjected to barrel polishing, and then an external electrode paste containing Cu powder and glass was applied to both end portions of the capacitor body, and baked at 850 C to form an external electrode. Thereafter, mineral Ni and ore (sn) were sequentially applied to the surface of the external electrode using an electrolytic roller machine to prepare a multilayer ceramic capacitor of 098109473 24 201007788 (SNoj - UO in Tables 1 to 3). <Evaluation> Then, the obtained multilayer ceramic capacitor was subjected to the following evaluation. (dielectric constant and dielectric loss)

For the dielectric constant and dielectric loss, the temperature is 25 VII, the frequency kHz, and the measured voltage is set to 〇〇1Vrms or 1 ν_ under the condition of ^Ma 1.0 capacitance> and according to the thickness and interior of the dielectric layer The electrode layer ^ has a static discharge. The dielectric constant and the dielectric loss were evaluated by setting the number of samples to 2^ based on the average value. Further, in the evaluation of the dielectric constant, the quasi-deviation σ is obtained, and the coefficient of variation (σ/χ) is obtained from the average value x. (Temperature characteristics of dielectric constant) The temperature characteristic of the dielectric constant is measured by the electrostatic capacitance in the range of _ 5 5 to 丨 5 〇. When the temperature characteristic of the dielectric constant satisfies X6S (in the range of C, within ±22% based on 25C), it is evaluated as 〇, and the case where it is not satisfied is evaluated as x. The evaluation of the temperature characteristics of the dielectric constant was carried out by setting the number of samples to 10 and calculating the average value. (Curie temperature) The Curie temperature is obtained as the temperature at which the dielectric constant reaches the maximum in the range in which the temperature characteristic of the dielectric constant is measured. (High temperature load test) The temperature load test is based on a temperature of 1〇5. (: or 125 ° C, the applied voltage is 6 V / / zm, 1 〇〇〇 hours. The number of samples in the high temperature load test 098109473 25 201007788 is set to 20 samples, will be 1 〇〇〇 In addition, regarding the above temperature, for the sample to be good, for the sample plate 81~110 is based on 25t, and is the average particle size of the crystal grains constituting the dielectric layer. Take "first' to the sample of the capacitor body after the shot: °100 and then use a scanning electron microscope to shoot (4) ❹ = rr in the photo ... surrounded by 2 ° ~ 3.. Two: select inside the circle and on the circumference Then, the image of each (10) is imaged: the area: the area of each particle is calculated and replaced with a straight k with the same area, and the average grain is obtained from the average value. 'The above-mentioned grinding system is carried out by first rough grinding the fracture surface using a diamond plate, and then grinding the sandpaper of the Lai. Then, 'grinding the diamond liquid coated on the hard polishing wheel, and then grinding the particle size For 〇·3 _ oxidized 35 abrasive particles coated on soft suspension On the light wheel, fine grinding is carried out. (弼 concentration · C2 / (C1 + C2)) Regarding the calcium concentration in the grain, a transmission electron microscope with elemental analysis equipment is used to form a laminated ceramic by ion milling. The crystal grain of the dielectric layer of the capacitor was polished to an elemental analysis of the crystal grains present on the polished surface until the extent of observation. The spot size of the electron beam was set to 5 nrn. From 098109473 26 201007788, the line drawn toward the center near the grain boundary of the grain is set at 4 to 5 points at substantially equal intervals from the grain boundary. Then, Ba, Ti, which are detected from each measurement point, are obtained.

The ratio of calcium when the total amount of Ca, V, Mg, RE (rare earth element) and Μη is 1% to 0%, and the average value of the calcium ratio determined from each measurement point is determined as the calcium concentration. - The grain size of the 35-concentration is selected as follows. First, a cross-section of a dielectric layer constituting a laminated ceramic capacitor was taken using a transmission electron microscope (a photograph of a polished surface obtained by grinding). Then, 20 30 enamel granules were formed on the upper edge of the photograph. Circle 'Using image processing to determine the area of each particle based on the contour of each grain located in the circle and on the circumference, and calculating the straightness when replaced with 8] of the same area; ^. Next, the diameter of the grain The crystal grains are in the range of ±30% of the average particle diameter as the crystal grains. Further, the total of the first crystal grains and the second crystal grains selected and measured from the respective crystal grains located in the circle and the circumference are obtained. The area is calculated as the value of C2/(C1 + C2) [•. Further, as described above, the center of the grain is the center of the grain (4), and the vicinity of the grain boundary of the so-called grain refers to The grain boundary of the grain rises to the inner side of the 5th surface. And the 'inscribed circle of the grain is taken into the computer by the image reflected by the transmission electron microscope, and the grain is formed on the surface of the grain. The edge of the circle is 'into the circle' and determines the center of the grain. (X-ray diffraction: XRD) The ratio of the diffraction intensity of the (200) plane of the barium titanate to the diffraction intensity of the (002) plane showing the titanate of the square 098109473 27 201007788 is determined by using a tube having a Cuk-α: The x-ray diffraction device is measured in the range of angle 26 > two 44 to 46 'determined by the ratio of peak intensities. (Rare earth element, Mengzhi) difference in rare earth elements and manganese contained in crystal grains. The concentration was measured using a transmission electron microscope with an elemental analyzer (EDS). For the sample to be analyzed, the multilayer ceramic capacitor was ground to a level that can be observed by ion milling in the lamination direction. The first crystal grain determined by the measurement of the calcium concentration and the second first crystal grain and the second crystal grain selected by the measurement of the calcium concentration are respectively selected on the surface of the polished dielectric layer, and are respectively subjected to image processing according to the image The area of each particle was obtained from the profile, and the diameter when replacing the circle having the same area was calculated, and each crystal grain was set to be in the range of ±3〇% of the average particle diameter determined by the above-described measurement method. Select 1 place separately The first and second crystal grains within the range. In addition, the grain-based portion of the surface layer portion of the analysis (from

The concentration of rare earth elements and manganese, and the concentration of rare earth elements and manganese at the position of nm! The branch size of the electron beam based on the element b obtained by each of the above-described methods is set to 1 to 3 nm. The grain boundary of the other grain profile is 3 nm. The depth of the surface layer portion of the second crystal grain is 1 〇' the rare earth element of the second crystal grain and the concentration of 098109473 201007788, and the sharp concentration of the surface layer of each crystal grain is subtracted from the depth of 10 legs. The concentration difference obtained by the impurity concentration and the rare earth element concentration in the surface layer portion of each crystal grain are subtracted from the concentration of the rare earth element at a position of 1 G nm. Specifically, this operation is performed for each of 10 pairs of crystal grains, and the average value of the crystal grains is calculated for a total of 20 values obtained from the respective crystal grains. Further, in the samples shown in Tables 2, 4, 5, and 7 to 1G, the rare earth element and manganese contained in the crystal grains of the dielectric ceramics constituting the laminated ceramic capacitor of the present invention (4) The change in concentration showed the same tendency as the sample n 〇 3. (Composition analysis) The composition analysis of the sample of the obtained sintered body was performed by inductively coupled ICP (ICP) analysis or atomic absorption spectroscopy. Ordering 'Led's dielectric screaming _ acid and Weiner mixed and added to the melt dissolved in hydrochloric acid, first using atomic absorption analysis for qualitative analysis of the elements contained in the dielectric shout. Then, for specific Each element is diluted with a standard solution and quantified by ICP emission spectrometry, and the amount of oxygen is determined by setting the valence of each element to the valence shown in the periodic table. The composition of the formulation and the calcination temperature are shown in Tables 1 to 3, and the composition of each element in the sintered body in terms of oxide is shown in Tables 4 to 6, and the thickness of the dielectric layer after calcination and the ratio of crystal grains ( C2/(C1 + C2)), average particle size 098109473 29 201007788 The difference between the peak intensity ratio of the cubic crystal and the tetragonal crystal, the Curie temperature, the surface portion of the crystal grain and the depth of the surface layer at a depth of 10 nm by x-ray diffraction, The results (temperature characteristics, dielectric loss, dielectric constant (determined from the temperature characteristics of the electrostatic capacitance), and the lifetime in the high-temperature load test) are shown in Tables 7 to 12. 098109473 30 201007788 [Table i ]

Sample No. BT powder BCT powder v2〇f ΜβΟ MnCO, RE ΤΤ) 4〇7 Calcination temperature Molmers Moramole element Moermol °c *1 50 50 0.1 0.5 0.3 Y 0.5 0 1130 2 50 50 0.1 0.5 0.3 Y 0.5 0.05 1130 3 50 50 0.1 0.5 0.3 Y 0.5 0.1 1130 4 50 50 0.1 0.5 0.3 Y 0.5 0.15 1130 5 50 50 0.1 0.5 0.3 Y 0.5 0.2 1130 *6 50 50 0.1 0.5 0.3 Y 0.5 0.3 1130 *7 50 50 0 0.5 0.3 Y 0.5 0.1 1130 8 50 50 0.02 0.5 0.3 Y 0.5 0.1 1130 9 50 50 0.05 0.5 0.3 Y 0.5 0.1 1130 10 50 50 0.08 0.5 0.3 Y 0.5 0.1 1130 11 50 50 0.12 0.5 0.3 Y 0.5 0.1 1130 12 50 50 0.15 0.5 0.3 Y 0.5 0.1 1130 13 50 50 0.2 0.5 0.3 Y 0.5 0.1 1130 *14 50 50 0.3 0.5 0.3 Y 0.5 0.1 1130 *15 50 50 0.1 0.1 0.3 Y 0.5 0.1 1130 16 50 50 0.1 0.2 0.3 Y 0.5 0.1 1130 17 50 50 0.1 0.3 0.3 Y 0.5 0.1 1130 18 50 50 0.1 0.6 0.3 Y 0.5 0.1 1130 19 50 50 0.1 0.8 0.3 Y 0.5 0.1 1130 *20 50 50 0.1 1 0.3 Y 0.5 0.1 1130 *21 50 50 0.1 0.5 0 Y 0.5 0.1 1130 22 50 50 0.1 0.5 0.1 Y 0.5 0.1 1130 23 50 50 0.1 0.5 0.2 Y 0.5 0.1 1130 24 50 50 0.1 0.5 0.4 Y 0.5 0.1 1130 25 50 50 0.1 0.5 0.5 Y 0.5 0.1 1130 *26 50 50 0.1 0.5 0.6 Y 0.5 0.1 1130 *27 50 50 0.1 0.5 0.3 Y 0.1 0.1 1130 28 50 50 0.1 0.5 0.3 Y 0.3 0.1 1130 29 50 50 0.1 0.5 0.3 Y 0.4 0.1 1130 30 50 50 0.1 0.5 0.3 Y 0.6 0.1 1130 31 50 50 0.1 0.5 0.3 Y 0.8 0.1 1130 *32 50 50 0.1 0.5 0.3 Y 1 0.1 1130 33 50 50 0.1 0.5 0.3 Dy 0.5 0.1 1130 34 50 50 0.1 0.5 0.3 Ho 0.5 0.1 1130 35 50 50 0.1 0.5 0.3 Er 0.5 0.1 1130 *36 90 10 0.1 0.5 0.3 Y 0.5 0.1 1130 37 80 20 0.1 0.5 0.3 Υ 0.5 0.1 1130 38 70 30 0.1 0.5 0.3 Υ 0.5 0.1 1130 39 55 45 0.1 0.5 0.3 Υ 0.5 0.1 1130 * 40 40 60 0.1 0.5 0.3 Υ 0.5 0.1 1130 * The mark indicates a sample outside the scope of the present invention. 098109473 31 201007788 [Table 2] Sample BT powder BCT powder V2〇5 MgO MnC〇3 RE2O3 Tb4〇7 Calcination temperature No. Molmole Moramole element Moermol °c 41 80 20 0.02 0.5 0.3 Y 0.5 0.1 1130 42 70 30 0.02 0.5 0.3 Y 0.5 0.1 1130 43 55 45 0.02 0.5 0.3 Y 0.5 0.1 1130 44 80 20 0.05 0.5 0.3 Y 0.5 0.1 1130 45 70 30 0.05 0.5 0.3 Y 0.5 0.1 1130 46 55 45 0.05 0.5 0.3 Y 0.5 0.1 1130 47 80 20 0.08 0.5 0.3 Y 0.5 0.1 1130 48 70 30 0.08 0.5 0.3 Y 0.5 0.1 1130 49 55 45 0.08 0.5 0.3 Y 0.5 0.1 1130 50 80 20 0.05 0.5 0.3 Y 0.5 0.02 1130 51 70 30 0.05 0.5 0.3 Y 0.5 0.02 1130 52 55 45 0.05 0.5 0.3 Y 0.5 0.02 1130 53 80 20 0.05 0.5 0.3 Y 0.5 0.05 1130 54 70 30 0.05 0.5 0.3 Y 0.5 0.05 1130 55 55 45 0.05 0.5 0.3 Y 0.5 0.05 1130 56 80 20 0.05 0.5 0.3 Y 0.5 0.08 1130 57 70 30 0.05 0.5 0.3 Y 0.5 0.08 1130 58 55 45 0.05 0.5 0.3 Y 0.5 0.08 1130 59 70 30 0.05 0.3 0.3 Y 0.5 0.05 1130 60 70 30 0.05 0.6 0.3 Y 0.5 0.05 1130 61 70 30 0.05 0.5 0.2 Y 0.5 0.05 1130 62 70 30 0.05 0.5 0.4 Y 0.5 0.05 1130 63 70 30 0.05 0.5 0.3 Y 0.4 0.05 1130 64 70 30 0.05 0.5 0.3 Y 0.6 0.05 1130 65 50 50 0.05 0.5 0.3 Dy 0.5 0.05 1130 66 50 50 0.05 0.5 0.3 Ho 0.5 0.05 1130 67 50 50 0.05 0.5 0.3 Er 0.5 0.05 1130 68 80 20 0.05 0.5 0.3 Y 0.5 0.02 1130 69 70 30 0.05 0.5 0.3 Υ 0.5 0.02 1130 70 55 45 0.05 0.5 0.3 Υ 0.5 0.02 1130 71 80 20 0.05 0.5 0.3 Υ 0.5 0.05 1130 72 70 30 0.05 0.5 0.3 Υ 0.5 0,05 1130 73 55 45 0.05 0.5 0.3 Υ 0.5 0.05 1130 74 80 20 0.05 0.5 0.3 Υ 0.5 0.08 1130 75 70 30 0.05 0.5 0.3 Υ 0.5 0.08 1130 76 55 45 0.05 0.5 0.3 Υ 0.5 0.08 1130 77 50 50 0.05 0.5 0.3 Υ 0.5 0.05 1130 78 70 30 0.05 0.5 0.3 Υ 0.5 0.05 1120 79 70 30 0.05 0.5 0.3 Υ 0.5 0.05 1130 80 70 30 0.05 0.5 0.3 Υ 0.5 0.05 1135 * The mark indicates a sample outside the scope of the present invention. 32 098109473 201007788 [Table 3]

Sample No. BT powder BCT powder V2〇5 MgO MnC03 RE2〇3 Tb4〇7 Calcination temperature Molmers Moramole element Moermol °c *81 50 50 0.1 0.5 0.3 Y 0.5 0 1130 82 50 50 0.1 0.5 0.3 Y 0.5 0.05 1130 83 50 50 0.1 0.5 0.3 Y 0.5 0.1 1130 *84 50 50 0.1 0.5 0.3 Y 0.5 0.3 1130 *85 50 50 0 0.5 0.3 Y 0.5 0.1 1130 86 50 50 0.05 0.5 0.3 Y 0.5 0.1 1130 87 50 50 0.08 0.5 0.3 Y 0.5 0.1 1130 88 50 50 0.2 0.5 0.3 Y 0.5 0.1 1130 *89 50 50 0.3 0.5 0.3 Y 0.5 0.1 1130 *90 50 50 0.1 0.1 0.3 Y 0.5 0.1 1130 91 50 50 0.1 0.2 0.3 Y 0.5 0.1 1130 92 50 50 0.1 0.3 0.3 Y 0.5 0.1 1130 93 50 50 0.1 0.6 0.3 Y 0.5 0.1 1130 94 50 50 0.1 0.8 0.3 Y 0.5 0.1 1130 *95 50 50 0.1 1 0.3 Y 0.5 0.1 1130 *96 50 50 0.1 0.5 0 Y 0.5 0.1 1130 97 50 50 0.1 0.5 0.2 Y 0.5 0.1 1130 *98 50 50 0.1 0.5 0.6 Y 0.5 0.1 1130 *99 50 50 0.1 0.5 0.3 Y 0.1 0.1 1130 100 50 50 0.1 0.5 0.3 Y 0,4 0.1 1130 101 50 50 0.1 0.5 0.3 Y 0.6 0.1 1130 *102 50 50 0.1 0.5 0.3 Y 1 0.1 1130 103 50 50 0.1 0.5 0,3 Dy 0.5 0.1 1130 104 50 50 0.1 0.5 0.3 Ho 0.5 0.1 1130 105 50 50 0.1 0.5 0.3 Er 0.5 0.1 1130 *106 90 10 0.1 0.5 0.3 Y 0.5 0.1 1130 107 80 20 0.1 0.5 0.3 Υ 0.5 0.1 1130 108 70 30 0.1 0.5 0.3 Υ 0.5 0.1 1130 109 55 45 0.1 0.5 0.3 Υ 0.5 0.1 1130 * 110 40 60 0.1 0.5 0.3 Υ 0.5 0.1 1130 * The mark indicates a sample outside the scope of the present invention. 098109473 33 201007788 [Table 4] ^ σ χτΛ V2〇s MgO MnO RE2〇i Tb4〇7 〇 IN IN Ο. Mo Mo Mo Mo Mo Mo Mo *1 0.1 0.5 0.3 Y 0.5 0 2 0.1 0.5 0.3 Υ 0.5 0.05 3 0.1 0.5 0.3 Υ 0.5 0.1 4 0.1 0.5 0.3 Υ 0.5 0.15 5 0.1 0.5 0.3 Υ 0.5 0.2 *6 0.1 0.5 0.3 Υ 0,5 0.3 *7 0 0.5 0.3 Υ 0.5 0.1 8 0.02 0.5 0.3 Υ 0.5 0.1 9 0.05 0.5 0.3 Υ 0.5 0.1 10 0.08 0.5 0.3 Υ 0.5 0.1 11 0.12 0.5 0.3 Υ 0.5 0.1 12 0.15 0.5 0.3 Υ 0.5 0.1 13 0.2 0.5 0.3 Υ 0.5 0.1 * 14 0.3 0.5 0.3 Υ 0.5 0.1 * 15 0.1 0.1 0.3 Υ 0.5 0.1 16 0.1 0.2 0.3 Υ 0.5 0.1 17 0.1 0.3 0.3 Υ 0.5 0.1 18 0.1 0.6 0.3 Υ 0.5 0.1 19 0.1 0.8 0.3 Υ 0.5 0.1 * 20 0.1 1 0.3 Υ 0.5 0.1 * 21 0.1 0.5 0 Υ 0.5 0.1 22 0.1 0.5 0.1 Υ 0.5 0.1 23 0.1 0.5 0.2 Υ 0.5 0.1 24 0.1 0.5 0.4 Υ 0.5 0.1 25 0.1 0.5 0.5 Υ 0.5 0.1 * 26 0.1 0.5 0.6 Υ 0.5 0.1 * 27 0.1 0.5 0.3 Υ 0.1 0.1 28 0.1 0.5 0.3 Υ 0.3 0.1 29 0.1 0.5 0.3 Υ 0.4 0.1 30 0.1 0.5 0.3 Υ 0.6 0.1 31 0.1 0.5 0.3 Υ 0.8 0.1 *32 0.1 0.5 0.3 Υ 1 0.1 33 0 .1 0.5 0.3 Dy 0.5 0.1 34 0.1 0.5 0.3 Ho 0.5 0.1 35 0.1 0.5 0.3 Er 0.5 0.1 * 36 0.1 0.5 0.3 Υ 0.5 0.1 37 0.1 0.5 0.3 Υ 0.5 0.1 38 0.1 0.5 0.3 Υ 0.5 0.1 39 0.1 0.5 0.3 Υ 0.5 0.1 *40 0.1 0.5 0.3 Υ 0.5 0.1 * The mark indicates a sample outside the scope of the present invention. 34 098109473 201007788 [Table 5]

Sample No. ν2〇5 MgO ΜηΟ RE2O3 Τ1>4〇7 Moramole element Moermol 41 0.02 0.5 0.3 Υ 0.5 0.1 42 0.02 0.5 0.3 Υ 0.5 0.1 43 0.02 0.5 0.3 Υ 0.5 0.1 44 0.05 0.5 0.3 Υ 0.5 0.1 45 0.05 0.5 0.3 Υ 0.5 0.1 46 0.05 0.5 0.3 Υ 0.5 0.1 47 0.08 0.5 0.3 Υ 0.5 0.1 48 0.08 0.5 0.3 Υ 0.5 0.1 49 0.08 0.5 0.3 Υ 0.5 0.1 50 0.05 0.5 0.3 Υ 0.5 0.02 51 0.05 0.5 0.3 Υ 0.5 0.02 52 0.05 0.5 0.3 Υ 0.5 0.02 53 0.05 0.5 0.3 Υ 0.5 0.05 54 0.05 0.5 0.3 Υ 0.5 0.05 55 0.05 0.5 0.3 Υ 0.5 0.05 56 0.05 0.5 0.3 Υ 0.5 0.08 57 0.05 0.5 0.3 Υ 0.5 0.08 58 0.05 0.5 0.3 Υ 0.5 0.08 59 0.05 0.3 0.3 Υ 0.5 0.05 60 0.05 0.6 0.3 Υ 0.5 0.05 61 0.05 0.5 0.2 Υ 0.5 0.05 62 0.05 0.5 0.4 Υ 0.5 0.05 63 0.05 0.5 0.3 Υ 0.4 0.05 64 0.05 0.5 0.3 Υ 0.6 0.05 65 0.05 0.5 0.3 Dy 0.5 0.05 66 0.05 0.5 0.3 Ho 0.5 0.05 67 0.05 0.5 0.3 Er 0.5 0.05 68 0.05 0.5 0.3 Υ 0.5 0.02 69 0.05 0.5 0.3 Υ 0.5 0.02 70 0.05 0.5 0.3 Υ 0.5 0.02 71 0.05 0·5 0.3 Υ 0.5 0.05 72 0,05 0.5 0.30.5 0.05 73 0.05 0.5 0.3 Υ 0.5 0.05 74 0.05 0.5 0.3 Υ 0.5 0.08 75 0.05 0.5 0.3 Υ 0.5 0.08 76 0.05 0.5 0.3 Υ 0.5 0.08 77 0.05 0.5 0.3 Υ 0.5 0.05 78 0.05 0.5 0.3 Υ 0.5 0.05 79 0.05 0.5 0.3 Υ 0.5 0.05 80 0.05 0.5 0.3 Υ 0.5 0.05 * marks indicate samples outside the scope of the present invention. 098109473 35 201007788 [Table 6] Sample No. V2〇5 MgO MnO RE2O3 Tb4〇7 Moramole Element Moermol*81 0.1 0.5 0.3 Y 0.5 0 82 0.1 0.5 0.3 Y 0.5 0.05 83 0.1 0.5 0.3 Y 0.5 0.1 *84 0.1 0.5 0.3 Y 0.5 0.3 *85 0 0.5 0.3 Y 0.5 0.1 86 0.05 0.5 0.3 Y 0.5 0.1 87 0.08 0.5 0.3 Y 0.5 0.1 88 0.2 0.5 0.3 Y 0.5 0.1 *89 0.3 0.5 0.3 Y 0.5 0.1 *90 0.1 0.1 0.3 Y 0.5 0.1 91 0.1 0.2 0.3 Y 0.5 0.1 92 0.1 0.3 0.3 Y 0.5 0.1 93 0.1 0.6 0.3 Y 0.5 0.1 94 0.1 0.8 0.3 Y 0.5 0.1 *95 0.1 1 0.3 Y 0.5 0.1 *96 0.1 0.5 0 Y 0.5 0.1 97 0.1 0.5 0.2 Y 0.5 0.1 *98 0.1 0.5 0.6 Y 0.5 0.1 *99 0.1 0.5 0.3 Y 0.1 0.1 100 0.1 0.5 0.3 Y 0.4 0.1 101 0.1 0.5 0.3 Y 0.6 0.1 *102 0.1 0.5 0.3 Y 1 0.1 103 0.1 0.5 0.3 Dy 0.5 0.1 104 0.1 0.5 0.3 Ho 0.5 0.1 105 0.1 0.5 0.3 Er 0.5 0.1 * 106 0.1 0.5 0.3 Υ 0.5 0.1 107 0.1 0.5 0.3 Υ 0.5 0.1 108 0.5 0.3 Υ 0.5 0.1 109 0.1 0.5 0.3 Υ 0.5 0.1 * 110 0.1 0.5 0.3 Υ 0.5 The 0.1* mark indicates a sample outside the scope of the present invention. 36 098109473 201007788

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High temperature load test #5 X 〇X 〇〇〇〇〇X 〇〇〇〇〇〇〇〇〇〇〇〇〇X)) I 〇〇〇〇〇〇〇〇〇〇〇〇〇〇X 〇〇〇〇 〇 Dielectric loss% I Vrms ο « 4 <N o 1__12^_1 ϊ-Η Dielectric constant coefficient of variation τ—< 00 o fS r—< rH in o r<i (N (N <s CN CS <N CN 1-4 CN <s (N *-H 4 ratio of dielectric constant #3 ^Τ) «-Η I> oo 〇\ (N cs 卜卜卜00 00 CS OO c4 00 Γ- ; 00 卜 I Vrms 3400 | 3700 3720 | 3740 | 3800 3900 3820 | 3800 1 3740 3730 | 3680 1 3610 | 3510 1 3430 3800 | 3750 I 3740 3660 | 3580 ] 3420 Concentration difference of rare earth elements #7 Atomic % inch · &lt ;N o F—H 〇\ o r- d >n 〇ΓΟ qor«H On d 卜 om <N t—< ot·^ ON d oo d 卜 o Mn concentration difference #6 Atomic % in ο Rn oo »-H ooo inch d ΓΛ 〇CS d ^«4 odooo O o inch o ΓΛ CS dooooo Curie temperature P w-><Ν s 100 OS Ui On 5: m cs 1—HS s rH ss rH Soo w-> ON oso ON w&gt ; On m 00 XRD #2 I 〇〇〇〇〇X 〇〇〇〇〇〇〇X 平均 average grain size of the grain βΤΏ. 0.26 | 0.25 0.25 I 0.25 I 0.25 0.25 0.21 Γ 0.22 ] 0.22 0.23 0.25 0.27 mo 0.32 0.25 | 0.25 I | 0.25 I | 0.25 I | 0.25 I 0.25 Grain ratio #C2/(Cl+C2) I Bu C> Bu o Bu o Bu o Bu od Bu o Bu o Bu o Bu dr ** o 卜d b o 卜 o 卜 o 卜 o 卜 o 卜 o 卜 o thickness of the dielectric layer "m r "H »-H »-H TH sample No. (N ro inch in 00 ON o rM CS 1-H 1-H * »r> Meal v〇00 ON o <N w?nr?*te«!!l?^«BH^w EH 2 嫦«!!枨嘱 Target轶!!| «名«?^-:?4 tons: 9# χ :^#ι->«!ί«κ--〇:!^*->When '『,000了Λ9,pslDi;1f:s# X :^-ww^«K--〇:!^ife.w S9xe«: 3lt46-^^w*i> 50%-wa, ov/«i轵一.^wta —Λ I^s^uv : ε# X - - ο - .寒&:4^«/A certain match &:: 阳买羿牵-0*^Select: 3# ^«W4no»wji^0\o^·,^ 2 Mu ,φ ΰ««w4° >sWJ.Kt/0 屮®?ro 嫦inr^D 'Ϊ3:牝

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MnO conversion is 0.2 to 0.4 m, and at least one rare earth element selected from the group consisting of 自, 镝, 鈥, and 斜 is set to 〇4 to 0.6 mol in terms of RE2〇3, and 铽 is set to Tb407. The conversion is 〇.〇2~〇.〇8mole sample N〇5〇~80 The dielectric constant when the AC voltage is set to 1 V is the dielectric when the AC voltage is set to 〇.〇1 V 1.5 times or less of the constant. Further, the average particle diameter of the crystal grains constituting the dielectric layer is set to be in the range of 0.14 to 0.28 098109473 43 201007788 /zm, and samples n〇.2 to 5, 8 to 12, 16 to 19, 22 to 25, 28 to 31, 33~35, 37~39, 41~77, 79, 80, 82, 83' 86~88, 91~94, 97, 100, 1〇1, 103~1〇5 and 1〇7~1〇 The dielectric constant of the 9-series is 35 〇〇 or more, the dielectric loss is 12.5% or less, the temperature characteristic of the dielectric constant satisfies X6S, and the dielectric constant when the AC voltage is set to 1 v is when the AC voltage is set to v. The dielectric constant is 1.9 times or less. Further, 'as a composition of a dielectric ceramic constituting a dielectric layer, 轼 is a sample of 0.05 to 〇〇8 mol in terms of Tb407 N〇2, 53~67, 71~ ribs and 82 series The coefficient of variation of the dielectric constant is 〇9 or less, and the unevenness is small. Further, as is clear from Fig. 5(a), the concentration of the 'surface layer' in the first crystal grain and the second crystal grain of the electric layer in the multilayer ceramic capacitor constituting the sample N〇3 is reduced by 10 nm. The concentration difference of the positional (Mn) concentration is 〇3 atoms/〇, and the concentration of the rare earth element (γ) in the surface layer is subtracted from the concentration of the rare earth element (γ) at the position of the concentration of the wire (10) atom. /. the above. Further, other samples of the present invention (samples N〇2, 4, 5, 8 to 13, 16 to 19, Θ 22 to 25, 28 to 3, 33 to 35, 37 to 39, 41 to 80, 82, 83, 86 to 88, 91 to 94, 97, 1 〇〇, 101, 1 〇 3 to 1 〇 5 and 1 〇 7 to 1 〇 9), and also have the following concentration difference similarly to sample No. 3: surface layer _ Concentration difference obtained by subtracting the concentration of manganese (Mn) at a depth of 10 nm from the concentration of manganese (Mn) at a depth of 10 nm or less and the concentration of rare earth elements in the surface layer minus the concentration of rare earth element at a depth of 10 nm It is 0.7 atom% or more. In addition, as a composition of the dielectric material constituting the dielectric layer, the vanadium of the titanium silicate which constitutes 098109473 44 201007788 barium titanate is set to 0 05 to 〇J Mo in the range of V2 〇 5 , Magnesium is 0.2 to 0.8 mol in terms of MgO, and manganese is at least 1 rare earth element selected from lanthanum, cerium, lanthanum and cerium in terms of MnO. It is set to 〇4 to 〇6 mol in terms of RE2〇3, and the money is set to 0.05~〇.1 mol in terms of Tb4〇7, and the average of the jth die and the second die Sample No. 82, 83, 86 to 88, 91 to 94, 97, 1 〇〇, 1 (U, 103 to 1 〇 5 and 1 〇 7 to 1 〇 9) having a particle diameter of 0.14 to 0.19, The temperature of the temperature-temperature load test was set to 125 ° C, and the voltage was set to 6 V, which was not more than 1000 hours. The samples N〇i, 6, and 7, which are outside the scope of the present invention. 14, 15, 20, 2, 26, 27, 32, 36, 40, 81, 84, 85, 89, 90, 95, 96, 98 99 102, 1〇6 and 110 do not satisfy any of the following characteristics: room temperature The dielectric constant is more than 3500, and the dielectric loss is 125%. The temperature characteristic of the dielectric constant satisfies X6S, the dielectric constant when the AC voltage is set to i V is, the AC voltage is set to 2 times or less of the dielectric constant at 〇.〇1 v, and the high-temperature load test In addition, the concentration of the woven rare earth element (7) of the sample Να1 in which the crystal structure is a core-shell structure, the Curie temperature is 丨, and the dielectric ceramic (4) is the dielectric layer is observed. b) It can be seen that the concentration of the surface layer minus the concentration of the clock at a depth of 10 nm gives a concentration difference of 〇$ atom%, and the rare earth element (7) concentration in the surface layer is subtracted from the depth of 4 1 〇 nm. The difference in concentration of element (7) is 0.8 atomic 〇/〇. 098109473 45 201007788 In addition, the sample No. 6 and the rare earth element (7) whose intensity is smaller than the square wave peak intensity and the Curie temperature is 91 °C. When the concentration is observed, it can be seen from Fig. 5(c) that the sharp concentration of the surface layer is subtracted from the sharp concentration at the position of the depth of nm, and the difference in the density of the rare earth element (γ) in the surface layer is subtracted from the depth. It is obtained from the concentration of rare earth element (Y) at a position of 10 nm. The degree difference is less than 〇 2 atom%. Further, in the crystal grains constituting the dielectric layer of the fabricated ceramic capacitor, (the concentration of the second crystal grains is 0.5 to 1.5 atom% in the analysis range. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of a multilayer ceramic capacitor of the present invention. Fig. 2 is an enlarged view of a dielectric layer constituting the multilayer ceramic capacitor shown in Fig. 1 and showing crystal grains and crystals. Schematic diagram of the boundary. Figure 3 is an X-ray diffraction pattern of sample No. 3 in the examples. Fig. 4 is a V. graph showing the temperature characteristics of the electrostatic capacitance of the sample No. 3 in the example. Fig. 5(a) is a graph showing changes in the concentration of rare earth elements and manganese contained in the crystal grains of the dielectric ceramics of the laminated ceramic capacitor of the sample n〇.3 in the example 'Fig. 5(b) The graph showing the change in the concentration of rare earth elements and manganese contained in the crystal grains of the dielectric ceramic constituting the laminated ceramic capacitor of the sample No. 1 in the example is shown in Fig. 5(c). A graph showing changes in the concentration of rare earth elements and manganese contained in the grains of the dielectric ceramic of the multilayer ceramic capacitor of the sample n〇.6. 098109473 46 201007788 [Description of main components] 1 Capacitor body 3 External electrode 5 Dielectric layer 7 Internal electrode layer 9 Grain 9a First grain 9b Second grain 11 Grain boundary phase

098109473 47

Claims (1)

201007788 VII. Patent application scope: 1.- Multilayer ceramic capacitors, which are formed by alternately laminating a dielectric f layer and an internal electrode layer. The dielectric system is composed of titanic acid (four) and contains mμ. At least the choice of money, self-discipline, 镝, 鈥 and !! The above-mentioned laminated ceramic capacitor is characterized in that: Θ the above dielectric ceramics is 'relative to the titanium 100 mer which constitutes the titanic acid pin, and contains: ' to v205 The above calculation is 〇〇2 to 〇2 莫, and the above lock is 〇2 to 〇8 摩尔 in terms of MgO, and the above-mentioned clock of W~〇.5 莫 in Mn0 conversion, 鈥 and bait The above-mentioned selection of RE2〇3 for the difference is 〇3~〇8 Moer's self-discipline, at least one of the above-mentioned rare earth elements, and the above-mentioned money in the range of Tb4〇7 is 〇〇2~〇2 Further, 结晶 the crystal system constituting the above-mentioned dielectric ceramics has a first crystal group which has the above-mentioned acid strontium as a main component, and the concentration of the upper lying is 0.2 atom two and ητ is taken as Φ ^ And U and the second crystal group are composed of the second crystal grains having the above-mentioned barium titanate (tetra) and the concentration of the above sentence is 0.4 atom% or more, and the area of the dielectric is set to C1. , + C2) is 〇.3 〇.7 The first crystal grain observed on the polished surface of the terracotta terracotta has the area of the second crystal grain At C2, C2/(C1 098109473 48 201007788 is shown in the x-ray diffraction diagram of the above-mentioned dielectric ceramics, showing the cubic crystal of the acidity lock (independently, the degree of winding is described in the square-square barium titanate) 〇〇 2) the diffraction intensity of the surface, and the Curie temperature is 95 to 1 〇 5 art. 2. The multilayer ceramic capacitor of the first application of the patent application, wherein the first crystal grain and the second crystal The average particle diameter of the granules is 0.M~(4)(4). 3. The laminated terracotta according to item 1 of the patent application, wherein the above C2/(C1 + C2) is 0.4 to 〇6. (· ... 4·如帽The laminated (four) capacitor of the first or third aspect of the patent, wherein the upper dielectric (four) towel, (4) the titanium (10) material constituting the barium titanate, comprises: 〇〇2~〇 in V2〇5 conversion 〇8 Moer's above hunger, in terms of shun conversion, 〇.3~〇6莫耳上赖, in terms of 0 (four) ~ Μ 耳 上述 上述 猛 猛 猛 猛 猛 猛 猛 猛 猛 猛 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 At least one of the above-mentioned rare earth elements' of the self-discipline, shop, and choice of 〇ό莫耳, and the above-mentioned money of 〇〇2~〇〇8mol in the conversion of Tb4〇7. In the electric ceramics, the relative layer is filled with the capacitor. Among them, the above-mentioned dielectric 〇 〇 hopper A and the titanium silicate constituting the above-mentioned barium titanate contain the Tb4o7 refueling as α〇5~_莫耳上6·如申: The laminated ceramic capacitor of the first item of the patent scope, wherein the dielectric ceramic is compared with 椹 and 肀, and 丨 is converted to titanium titanate of barium titanate by (10). The above-mentioned manganese is contained in an amount of 0.2 to 0.8 mol, and the above-mentioned magnesium is 0.2 to 0.3 mol in terms of MnO, which is 0.4 in terms of RE203, in the range of 0.05 to 0.1 mol of the above vanadium, 098109473 49 201007788. At least one of the above rare earth elements selected from the group consisting of ruthenium, osmium, iridium and bait, and the above-mentioned ruthenium of 0.05 to 0.1 mol in terms of Tb407; and the first crystal grain and the second crystal The average particle size of the particles is 0.14~0.19 // m ° 098109473 50