JP5541318B2 - Dielectric ceramic composition and ceramic electronic component - Google Patents

Description

  The present invention relates to a dielectric ceramic composition and a ceramic electronic component in which the dielectric ceramic composition is applied to a dielectric layer. In particular, the dielectric ceramic exhibiting good characteristics even when the dielectric layer is thinned. The present invention relates to a body porcelain composition and a ceramic electronic component.

  A multilayer ceramic capacitor as an example of a ceramic electronic component is widely used as a small-sized, high-performance, high-reliability electronic component, and a large number of electric capacitors and electronic devices are used. In recent years, with the miniaturization and high performance of devices, the demand for further miniaturization, higher performance, and higher reliability of multilayer ceramic capacitors has become increasingly severe.

  In response to such demands, the dielectric layers of multilayer ceramic capacitors are being made thinner and multilayered. However, if the particle diameter of the dielectric particles is reduced in order to reduce the thickness of the dielectric layer, there is a problem that a desired characteristic cannot be obtained because the relative permittivity is lowered.

  Patent Document 1 discloses that in a multilayer ceramic capacitor having a dielectric layer composed of barium titanate crystal particles and barium calcium titanate crystal particles, the barium titanate crystal particles and barium calcium titanate crystal particles are 2 The inclusion of various types of rare earth elements and other components is described. It is described that this multilayer ceramic capacitor has a high insulation resistance, and there is little decrease in insulation resistance with time change in a high-temperature load test.

  However, the thickness of the dielectric layer of the multilayer ceramic capacitor described in the example of Patent Document 1 is 2 μm, and it has been found that the problem cannot be solved when the dielectric layer is further thinned.

JP 2008-135638 A

  The present invention has been made in view of such a situation, and even when the dielectric layer is thinned, the dielectric ceramic composition exhibiting good characteristics, and the dielectric ceramic composition is provided in the dielectric layer. An object is to provide an applied ceramic electronic component.

In order to achieve the above object, the dielectric ceramic composition according to the present invention comprises:
A compound having a perovskite type crystal structure represented by the general formula ABO ₃ (A is at least one selected from Ba, Ca and Sr, and B is at least one selected from Ti, Zr and Hf), Containing as a main component,
With respect to 100 moles of the compound, in terms of each element,
0.6 to 2.0 mol of Mg oxide,
0.010 to 0.6 mol of an oxide of Mn and / or Cr,
0.010 to 0.2 mol of at least one oxide selected from the group consisting of V, Mo and W,
0.10 to 1.0 mol of an oxide of R1 (R1 is at least one selected from the group consisting of Y, Yb, Er and Ho),
0.10 to 1.0 mol of an oxide of R2 (R2 is at least one selected from the group consisting of Dy, Gd and Tb),
A component comprising 0.2 to 1.5 mol of a Ba oxide and / or a Ca oxide and a Si oxide is contained as a subcomponent.

In the present invention, by controlling the content of the main component and the subcomponent within the above range, the solid solution state of ABO ₃ which is the main component of the metal elements (particularly R1 and R2) of each subcomponent is controlled. Can do. As a result, even when the dielectric layer is thinned, a dielectric ceramic composition having favorable characteristics (for example, relative dielectric constant, dielectric loss, CR product, capacity temperature characteristic and high temperature load life) is obtained. be able to.

  Preferably, 0.50 <β / (α + β) <0.90 where the content of the R1 oxide in terms of R1 is α mol and the content of the R2 oxide in terms of R2 is β mol. , 0.2 ≦ (α + β) ≦ 1.5 is satisfied.

By setting α and β within the above range, the solid solution state of R1 and R2 in ABO ₃ can be made more preferable. As a result, the above-described effects can be further enhanced.

  Preferably, in the component, when the molar ratio of Ba is a, the molar ratio of Ca is b, and the molar ratio of Si is c, a, b and c are a + b + c = 1, a + b ≦ c and 0 ≦ a ≦ 0.5, 0 ≦ b ≦ 0.5, and 0.5 ≦ c ≦ 0.8 are satisfied.

  By setting the ratio of each metal element in the component containing Ba or the like within the above range, the characteristics can be further improved.

  Preferably, the relationship of (α + β) /m≦10.5 is satisfied, where the content of each component in terms of each metal element is mmol.

  By setting the content of the oxides of R1 and R2 and the content of the component containing Ba or the like to the above relationship, in particular, the firing temperature can be lowered, and low-temperature firing is possible.

  Preferably, R1 is Y and R2 is Dy. The effect mentioned above can further be heightened by using said element as R1 and R2.

Preferably, the ABO ₃ is BaTiO ₃ . By doing so, it is possible to obtain a dielectric ceramic composition having a large capacity and high reliability.

  In addition, a ceramic electronic component according to the present invention includes a dielectric layer composed of the dielectric ceramic composition according to any one of the above and an electrode. Although it does not specifically limit as a ceramic electronic component, A multilayer ceramic capacitor, a piezoelectric element, a chip inductor, a chip varistor, a chip thermistor, a chip resistance, and other surface mount (SMD) chip type electronic components are illustrated.

FIG. 1 is a cross-sectional view of a multilayer ceramic capacitor according to an embodiment of the present invention.

  Hereinafter, the present invention will be described based on embodiments shown in the drawings.

Multilayer ceramic capacitor 1
As shown in FIG. 1, a multilayer ceramic capacitor 1 as an example of a multilayer ceramic electronic component includes a capacitor element body 10 having a configuration in which dielectric layers 2 and internal electrode layers 3 are alternately stacked. The internal electrode layers 3 are laminated so that the end faces are alternately exposed on the surfaces of the two opposite ends of the capacitor element body 10. The pair of external electrodes 4 are formed at both ends of the capacitor element body 10 and are connected to the exposed end surfaces of the alternately arranged internal electrode layers 3 to constitute a capacitor circuit.

  The shape of the capacitor element body 10 is not particularly limited, but is usually a rectangular parallelepiped as shown in FIG. Moreover, there is no restriction | limiting in particular also in the dimension, What is necessary is just to set it as a suitable dimension according to a use.

Dielectric layer 2
The dielectric layer 2 is composed of a dielectric ceramic composition according to this embodiment. The dielectric ceramic composition according to the present embodiment has, as a main component, a general formula ABO ₃ (A is at least one selected from Ba, Ca and Sr, and B is at least one selected from Ti, Zr and Hf. It is a compound represented by this. The dielectric ceramic composition has dielectric particles whose main component is ABO ₃ .

The ABO _3, for example, _{{(Ba (1-x-} y) Ca x Sr y) O} u (Ti (1-z) Zr z) v is expressed by _{O 2} compounds. Note that u, v, x, y, and z are all in an arbitrary range, but are preferably in the following ranges.

  In the above formula, x is preferably 0 ≦ x ≦ 0.1, more preferably 0 ≦ x ≦ 0.05. x represents the number of Ca atoms, and by setting x within the above range, the capacity temperature coefficient and the relative dielectric constant can be arbitrarily controlled. If x is too large, the dielectric constant tends to be low. In the present invention, Ca may not necessarily be included.

  In the above formula, y is preferably 0 ≦ y ≦ 0.1, more preferably 0 ≦ y ≦ 0.05. y represents the number of Sr atoms, and the capacitance temperature coefficient and the relative dielectric constant can be arbitrarily controlled by setting y in the above range. If y is too large, the relative permittivity tends to decrease or the temperature characteristics tend to deteriorate. In the present invention, Sr does not necessarily have to be included.

  In the above formula, z is preferably 0 ≦ z ≦ 0.2, more preferably 0 ≦ z ≦ 0.18. z represents the number of Zr atoms, and sinterability and reduction resistance can also be improved by setting z within the above range. If z is too large, the relative permittivity tends to decrease or the temperature characteristics tend to deteriorate. In the present invention, Zr may not necessarily be included.

In this embodiment, as ABO ₃ , barium titanate (preferably represented by the composition formula Ba _u Ti _v O ₃ and u / v is 0.994 ≦ u / v ≦ 1.002) is particularly used. It can be used suitably.

  In the perovskite crystal structure, c / a indicating the ratio of the c-axis lattice constant to the a-axis lattice constant is preferably 1.0085 or more. When c / a is too small, when the crystal particle diameter of the dielectric particles is reduced, the relative dielectric constant tends to be significantly reduced.

Note that c / a of all dielectric particles need not satisfy the above range. That is, for example, particles having a low c / a (cubic system) and particles having a high c / a (tetragonal system) may coexist in the ABO ₃ raw material powder. It is sufficient that c / a is in the above range.

  The dielectric ceramic composition according to the present embodiment includes an oxide of R1 (R1 is at least one selected from Y, Yb, Er, and Ho) as a subcomponent in addition to the above-described main component, R2 (R2 is at least one selected from Dy, Gd and Tb), Mg oxide, at least one oxide selected from V, Mo and W, Ba oxide and / or Or a component composed of an oxide of Ca and an oxide of Si.

When the content of the oxide of R1 is α, α is preferably 0.10 to 1.0 mol, more preferably 0.2 to 0.8 mol in terms of R1 element, with respect to 100 mol of ABO _3. It is. If α is too large, the dielectric constant tends to decrease. Conversely, if the amount is too small, the reliability tends to deteriorate. R1 is at least one selected from Y, Yb, Er and Ho, and is particularly preferably Y.

When the content of the oxide of R2 is β, β is preferably 0.10 to 1.0 mol, more preferably 0.2 to 0.8 mol in terms of R2 element with respect to 100 mol of ABO _3. It is. When β is too large, the capacity change rate with respect to temperature tends to increase. On the other hand, if the amount is too small, it tends to be difficult to ensure reliability. R2 is at least one selected from Dy, Gd and Tb, and particularly preferably Dy.

  Α and β preferably satisfy the relationship of 0.50 ≦ β / (α + β) ≦ 0.90 and 0.20 <(α + β) <1.5. More preferably, 0.6 ≦ β / (α + β) ≦ 0.83 and 0.5 ≦ (α + β) ≦ 1.2. If β / (α + β) is too large, the dielectric loss (tan δ) tends to deteriorate, and if it is too small, the life tends to be inferior. If (α + β) is too large, the desired dielectric constant tends not to be obtained, and if it is too small, tan δ tends to increase.

In the present embodiment, sub-component metal elements such as R1 and R2 are dissolved in dielectric particles whose main component is ABO ₃ . The dielectric particles may be partly solid solution or have a complete solid solution structure.

  When R2 is contained in the dielectric particles, the reliability can be improved while keeping the relative dielectric constant good, but the capacity-temperature characteristics tend to deteriorate. Moreover, this tendency becomes more prominent as the dielectric layer becomes thinner. Therefore, by including R1 in the dielectric particles, it is possible to improve the capacity-temperature characteristics while maintaining reliability. Such an effect becomes prominent particularly when α and β satisfy the above relationship.

  Further, by controlling the solid solution state of R1 and R2, it is possible to suppress a decrease in the dielectric constant even if the crystal particle diameter of the dielectric particles is reduced.

The content of the Mg oxide is preferably 0.6 to 2.0 mol in terms of each element with respect to 100 mol of ABO ₃ . When there is too much content of said oxide, it exists in the tendency for a temperature characteristic to deteriorate. On the other hand, if the amount is too small, the sintering does not proceed sufficiently.

The content of the oxide of Mn and / or Cr is preferably 0.010 to 0.6 mol, more preferably 0.05 to 0.3, in terms of Mn and / or Cr with respect to 100 mol of ABO _3. Is a mole. When the content of Mn and / or Cr oxide is too large, the capacity change rate tends to increase. On the other hand, if the amount is too small, sufficient reduction resistance cannot be obtained and the reliability tends to deteriorate. In the present embodiment, Mn is preferable.

The content of at least one oxide selected from the group consisting of V, Mo and W is preferably 0.010 to 0.2 mol, more preferably in terms of V, Mo and W with respect to 100 mol of ABO _3. Is 0.02 to 0.15 mol. When there is too much content of said oxide, it exists in the tendency for insulation resistance to deteriorate. Conversely, if the amount is too small, the reliability tends to deteriorate. In the present embodiment, V is preferable.

The component consisting of Ba oxide and / or Ca oxide and Si oxide mainly has a role as a sintering aid. Further, when the content of the component is m, m is preferably 0.2 to 1.5 mol, more preferably 0.5 to 1 in terms of Ba, Ca and Si with respect to 100 mol of ABO _3. .5 moles. Note that it is not preferable to include a Si oxide (for example, SiO ₂ ) alone in the dielectric ceramic composition because the dielectric particles easily grow.

Further, in this embodiment, in the component, when the molar ratio of Ba is a, the molar ratio of Ca is b, and the molar ratio of Si is c, a, b and c are a + b + c = 1, a + b ≦ It is preferable that c and 0 ≦ a ≦ 0.5, 0 ≦ b ≦ 0.5, and 0.5 ≦ c ≦ 0.8 are satisfied. More preferably, a + b <c and 0 ≦ a ≦ 0.45, 0 ≦ b ≦ 0.45, and 0.55 ≦ c ≦ 0.8. That is, the ratio of Si (for example, SiO ₂ ) in the component is equal to or greater than the sum of the ratio of Ba and Ca (for example, BaO and CaO). By doing in this way, while improving sinterability, a dielectric constant can be raised.

  The crystal particle diameter of the dielectric particles contained in the dielectric ceramic composition according to the present embodiment is not particularly limited, but is preferably 0.1 to 0.3 μm in order to meet the demand for thinning the dielectric layer. . Moreover, the dielectric ceramic composition according to the present embodiment may further contain other components according to desired characteristics.

  The thickness of the dielectric layer 2 is not particularly limited, but is preferably 2.0 μm or less per layer. Although the minimum of thickness is not specifically limited, For example, it is about 0.4 micrometer.

  The number of laminated dielectric layers 2 is not particularly limited, but is preferably 20 or more, more preferably 50 or more, and particularly preferably 100 or more. The upper limit of the number of stacked layers is not particularly limited, but is about 2000, for example.

Internal electrode layer 3
The conductive material contained in the internal electrode layer 3 is not particularly limited, but a relatively inexpensive base metal can be used because the material constituting the dielectric layer 2 has reduction resistance. As the base metal used as the conductive material, Ni or Ni alloy is preferable. The Ni alloy is preferably an alloy of Ni and one or more elements selected from Mn, Cr, Co and Al, and the Ni content in the alloy is preferably 95% by weight or more. In addition, in Ni or Ni alloy, various trace components, such as P, may be contained about 0.1 wt% or less. The thickness of the internal electrode layer 3 may be appropriately determined according to the application and the like, but is usually 0.1 to 3 μm, particularly preferably about 0.2 to 2.0 μm.

External electrode 4
The conductive material contained in the external electrode 4 is not particularly limited, but in the present invention, inexpensive Ni, Cu, and alloys thereof can be used. The thickness of the external electrode 4 may be appropriately determined according to the application and the like, but is usually preferably about 10 to 50 μm.

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

First, as a raw material, a raw material powder of ABO ₃ contained as a main component in a dielectric ceramic composition, and a gel hydroxide slurry of a metal element contained as a subcomponent or an aqueous solution of the element are prepared.

The raw material powder of ABO ₃ is not particularly limited, and oxides of the above-described components, mixtures thereof, and composite oxides can be used. In addition, various compounds that become the above-described oxides and composite oxides by firing, For example, it can be appropriately selected from carbonates, oxalates, nitrates, hydroxides, organometallic compounds, and the like, and can be used as a mixture.

ABO ₃ raw materials are produced by various methods such as those produced by various liquid phase methods (for example, oxalate method, hydrothermal synthesis method, alkoxide method, sol-gel method, etc.) in addition to the so-called solid phase method. Can be used.

  For rare earth elements, it is preferable to prepare a gel hydroxide slurry of rare earth elements, and for other metal elements, a gel hydroxide slurry may be prepared or may be prepared as an aqueous solution. In addition, about the component containing Ba etc., it is preferable to prepare the gel-like hydroxide slurry or aqueous solution of each metal element in this component. On the other hand, it is not preferable to add in the form of a complex oxide of metal elements constituting the component or in the form of glass powder. This is because the addition in the form of a complex oxide tends to result in insufficient dispersion, and the above-described effects tend not to be obtained. Moreover, it is because the addition in the form of glass powder has the tendency for the effect mentioned above to be hard to be acquired since the particle diameter of glass powder is large.

Next, in this embodiment, the ABO ₃ raw material powder and the gel hydroxide slurry or aqueous solution of the subcomponent metal element obtained above are dispersed together with water using a medium stirring type disperser such as a bead mill. A raw material mixture is obtained. The conditions for dispersion are not particularly limited, but for example, it is preferable to use a medium having a diameter of 0.1 mm or less. In addition, you may perform preliminary dispersion | distribution before dispersion | distribution using a medium stirring disperser.

In this dispersion, the ABO ₃ raw material powder and the subcomponent (gel hydroxide or metal element in the aqueous solution) are uniformly dispersed while crushing the ABO ₃ raw material powder. In this dispersion, it is preferable to further improve the dispersibility of the raw material mixture by adding a hydrophilic dispersant. Examples of hydrophilic dispersants include polycarboxylic acid-based dispersants.

The obtained raw material mixture is dried by, for example, spray drying. In the raw material mixture after drying, the surface of the ABO ₃ particles is in a state of being coated with a gel-like hydroxide or a subcomponent metal element in an aqueous solution.

By preparing the raw material mixture through such steps, it is possible to control the solid solution of the subcomponent metal element with respect to the ABO ₃ particles in the heat treatment step and the firing step, which will be described later. An realized dielectric ceramic composition can be obtained. For example, it is possible to prevent the rare earth element from being excessively dissolved in the ABO ₃ particle by coating the rare earth element on the ABO ₃ particle in the form of a gel hydroxide. As a result, desired characteristics can be obtained.

Subsequently, the dried raw material mixture is heat treated. By performing this heat treatment, the subcomponent metal element coated on the surface of the ABO ₃ particle is more firmly fixed to the particle. The holding temperature in the heat treatment is preferably in the range of 400 to 900 ° C. The holding time is preferably 0.1 to 3.0 hours. In addition, you may perform simultaneously drying and heat processing of a raw material mixture.

  Since the raw material mixture is agglomerated after the heat treatment, the raw material mixture may be crushed to such an extent that the agglomeration is loosened. This crushing may be performed after preparing a dielectric layer paste described later.

  The particle diameter of the raw material mixture (dielectric raw material) after the heat treatment is usually about 0.1 to 1 μm in average particle diameter. Next, the dielectric material is made into a paint to prepare a dielectric layer paste. The dielectric layer paste may be an organic paint obtained by kneading a dielectric material and an organic vehicle, or may be a water-based paint.

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

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

  The internal electrode layer paste is obtained by kneading the above-mentioned organic vehicle with various conductive metals and alloys as described above, or various oxides, organometallic compounds, resinates, etc. that become the above-mentioned conductive materials after firing. Prepare. The internal electrode layer paste may contain a common material. The common material is not particularly limited, but preferably has the same composition as the main component.

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

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

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

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

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

  After removing the binder, the green chip is fired. In firing, the rate of temperature rise is preferably 200 to 2000 ° C./hour. The holding temperature at the time of firing is preferably 1300 ° C. or less, more preferably 1100 to 1250 ° C., and the holding time is preferably 0.5 to 8 hours, more preferably 2 to 3 hours. If the holding temperature is lower than the above range, the densification becomes insufficient. If the holding temperature exceeds this range, the electrode is interrupted due to abnormal sintering of the internal electrode layer, the capacity-temperature characteristic is deteriorated due to diffusion of the constituent material of the internal electrode layer, and the dielectric Reduction of the body porcelain composition is likely to occur.

The firing atmosphere is preferably a reducing atmosphere. As the atmosphere gas, for example, a mixed gas of N ₂ and H ₂ can be used by humidification.

In addition, the oxygen partial pressure during firing may be appropriately determined according to the type of the conductive material in the internal electrode layer paste, but when a base metal such as Ni or Ni alloy is used as the conductive material, The oxygen partial pressure is preferably 10 ⁻¹⁴ to 10 ⁻¹⁰ MPa. When the oxygen partial pressure is less than the above range, the conductive material of the internal electrode layer may be abnormally sintered and may be interrupted. Further, when the oxygen partial pressure exceeds the above range, the internal electrode layer tends to be oxidized. The temperature lowering rate is preferably 50 to 2000 ° C./hour.

  After firing in a reducing atmosphere, the capacitor element body is preferably annealed. Annealing is a process for re-oxidizing the dielectric layer, and thereby the IR life (insulation resistance life) can be remarkably increased, so that the reliability is improved.

The oxygen partial pressure in the annealing atmosphere is preferably 10 ⁻⁹ to 10 ⁻⁵ MPa. When the oxygen partial pressure is less than the above range, it is difficult to re-oxidize the dielectric layer, and when it exceeds the above range, oxidation of the internal electrode layer tends to proceed.

  The holding temperature at the time of annealing is preferably 1100 ° C. or less, particularly 900-1100 ° C. When the holding temperature is lower than the above range, the dielectric layer is not sufficiently oxidized, so that the IR is low and the IR life tends to be short. On the other hand, if the holding temperature exceeds the above range, not only the internal electrode layer is oxidized and the capacity is lowered, but the internal electrode layer reacts with the dielectric substrate, the capacity temperature characteristic is deteriorated, the IR is lowered, the IR Life is likely to decrease. Note that annealing may be composed of only a temperature raising process and a temperature lowering process. That is, the temperature holding time may be zero. In this case, the holding temperature is synonymous with the maximum temperature.

As other annealing conditions, the temperature holding time is preferably 0 to 20 hours, more preferably 2 to 4 hours, and the cooling rate is preferably 50 to 500 ° C./hour, more preferably 100 to 300 ° C./hour. . Further, as the annealing atmosphere gas, for example, humidified N ₂ gas or the like is preferably used.

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

  The binder removal treatment, firing and annealing may be performed continuously or independently.

  The capacitor element main body obtained as described above is subjected to end face polishing, for example, by barrel polishing or sand blasting, and the external electrode paste is applied and fired to form the external electrode 4. Then, if necessary, a coating layer is formed on the surface of the external electrode 4 by plating or the like.

  The multilayer ceramic capacitor of this embodiment manufactured in this way is mounted on a printed circuit board or the like by soldering or the like and used for various electronic devices.

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

  For example, in the embodiment described above, a multilayer ceramic capacitor is exemplified as the ceramic electronic component according to the present invention. However, the ceramic electronic component is not limited to the multilayer ceramic capacitor, and may be an electronic component having the above-described configuration. Anything is fine.

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

Example 1
First, BaTiO ₃ powder was prepared as a raw material powder for ABO ₃ (u / v = 1.000). C / a = 1.0095. As auxiliary components, gel hydroxide slurry was prepared for Y and Dy, and aqueous solutions were prepared for Mg, Mn, V, Ba and Ca. In addition, as a raw material of Si, a dispersion of colloidal silica with water (an aqueous dispersion of Si) was prepared. The addition amounts of the main component and the subcomponent were weighed so as to have the values shown in Table 1. Further, a, b and c in the component containing Ba and the like were weighed so as to be 0.3, 0.15 and 0.55, respectively.

Next, the BaTiO ₃ powder and the raw materials of the accessory components were preliminarily dispersed for 1 hour using a ball mill. The raw material mixture after the preliminary dispersion was dispersed for 48 hours using a bead mill filled with a medium having a diameter of 0.1 mm to prepare a raw material mixture. That is, BaTiO ₃ powder, gel hydroxide or aqueous solution of each element, and an aqueous dispersion of Si were dispersed. Further, as a dispersant, a polycarboxylic acid-based dispersant was added at 2.0 wt% with respect to 100 wt% of BaTiO ₃ .

  The obtained raw material mixture was dried at 250 ° C. by a spray dryer, and then heat-treated at 750 ° C. for 15 minutes in a rotary kiln. The raw material mixture after the heat treatment was used as a dielectric raw material.

  Next, the obtained dielectric material: 100 parts by weight, polyvinyl butyral resin: 10 parts by weight, dioctyl phthalate (DOP) as a plasticizer: 5 parts by weight, and alcohol as a solvent: 100 parts by weight with a ball mill The mixture was made into a paste to obtain a dielectric layer paste.

  In addition to the above, Ni particles: 44.6 parts by weight, terpineol: 52 parts by weight, ethyl cellulose: 3 parts by weight, and benzotriazole: 0.4 parts by weight are kneaded by three rolls to obtain a paste. To prepare an internal electrode layer paste.

  Then, using the dielectric layer paste prepared above, a green sheet was formed on the PET film so that the thickness after drying was 1.0 to 1.5 μm. Next, the electrode layer was printed in a predetermined pattern using the internal electrode layer paste thereon, and then the sheet was peeled off from the PET film to produce a green sheet having the electrode layer. Next, a plurality of green sheets having electrode layers were laminated and pressure-bonded to obtain a green laminated body, and the green laminated body was cut into a predetermined size to obtain a green chip.

  Next, the obtained green chip was subjected to binder removal treatment, firing and annealing under the following conditions to obtain a multilayer ceramic fired body.

  The binder removal treatment conditions were temperature rising rate: 25 ° C./hour, holding temperature: 260 ° C., temperature holding time: 8 hours, and atmosphere: in the air.

The firing conditions were a heating rate of 1000 ° C./hour, a holding temperature of 1170 ° C., and a holding time of 1 hour. The cooling rate was 1000 ° C./hour. The atmospheric gas was a humidified N ₂ + H ₂ mixed gas, and the oxygen partial pressure was 10 ⁻¹² MPa.

The annealing conditions were: temperature rising rate: 200 ° C./hour, holding temperature: 1000 ° C., temperature holding time: 2 hours, temperature falling rate: 200 ° C./hour, atmospheric gas: humidified N ₂ gas (oxygen partial pressure: 10 ⁻⁷ MPa).

  A wetter was used for humidifying the atmospheric gas during firing and annealing.

  Next, after polishing the end face of the obtained multilayer ceramic fired body by sandblasting, Cu was applied as an external electrode to obtain a sample of the multilayer ceramic capacitor shown in FIG. The size of the obtained capacitor sample was 3.2 mm × 1.6 mm × 0.6 mm, the thickness of the dielectric layer was about 0.9 μm, the thickness of the internal electrode layer was about 0.7 μm, and was sandwiched between the internal electrode layers The number of dielectric layers was 100.

  About the obtained capacitor | condenser sample, the dielectric constant, dielectric loss, CR product, a capacitance temperature characteristic, and the high temperature load lifetime (HALT) were measured by the method shown below, respectively.

Dielectric constant ε
The relative dielectric constant ε was measured on a capacitor sample at a reference temperature of 25 ° C. using a digital LCR meter (4274A manufactured by YHP) under the conditions of a frequency of 1 kHz and an input signal level (measurement voltage) of 0.5 Vrms. Calculated from the electric capacity (no unit). It is preferable that the relative dielectric constant is high. In this example, 2500 or more was considered good. The results are shown in Table 1.

Dielectric loss (tan δ)
The dielectric loss (tan δ) was measured for a capacitor sample at a reference temperature of 25 ° C. using a digital LCR meter (4274A manufactured by YHP) under the conditions of a frequency of 1 kHz and an input signal level (measurement voltage) of 0.5 Vrms. The dielectric loss is preferably as low as possible. In this example, 5.0% or less was considered good. The results are shown in Table 1.

The insulation resistance IR after applying a DC voltage of 6.3 V / μm to the capacitor sample for 1 minute at 20 ° C. was measured for the CR product capacitor sample using an insulation resistance meter (R8340A manufactured by Advantest). The CR product was measured by determining the product of the capacitance C (unit: μF) measured above and the insulation resistance IR (unit: MΩ). In this example, 1000 or more was considered good. The results are shown in Table 1.

Capacitance temperature characteristics (TC)
The capacitance at −55 to 85 ° C. was measured for the capacitor sample, the rate of change ΔC in capacitance was calculated, and it was evaluated whether the E5 standard X5R characteristic or B characteristic was satisfied. That is, it was evaluated whether the rate of change ΔC at 85 ° C. was within ± 15%. The results are shown in Table 1.

High temperature load life (HALT)
The capacitor sample was maintained at 160 ° C. in an applied DC voltage under an electric field of 9 V / μm, and the lifetime was measured to evaluate the high temperature load life. In this example, the time from the start of application until the insulation resistance drops by an order of magnitude was defined as the lifetime. In this example, the above evaluation was performed on 20 capacitor samples, and the average value was defined as the high temperature load life. The evaluation standard was good for 20 hours or more. The results are shown in Table 1.

  From Table 1, it was confirmed that when the content of Mg oxide is outside the range of the present invention (Sample Nos. 1 and 5), the relative permittivity, capacity-temperature characteristics, high temperature load life, etc. tend to deteriorate. . Further, when the contents of Mn and Cr oxides were outside the scope of the present invention (Sample Nos. 6 and 11), it was confirmed that the capacity-temperature characteristics, the high temperature load life, etc. tended to deteriorate. Furthermore, when the contents of V, Mo, and W oxides are outside the scope of the present invention (sample numbers 12 and 18), it was confirmed that the CR product and the high temperature load life tend to deteriorate.

  On the other hand, when the content of each oxide is within the range of the present invention (sample numbers 2 to 4, 7 to 10, and 13 to 17), it was confirmed that good characteristics were obtained.

Example 2
A multilayer ceramic capacitor sample was prepared in the same manner as in Example 1 except that the contents of the main component and the subcomponent were changed to those shown in Table 2, and the same characteristic evaluation as in Example 1 was performed. The results are shown in Table 2. Regarding Sample No. 41, a sample was prepared by using the glass powder consisting of BaO, CaO and SiO ₂ Metropolitan. The glass powder was prepared by wet-mixing BaCO ₃ , CaCO ₃ and SiO ₂ for 16 hours with a ball mill, drying, firing in air at 1150 ° C., and further wet pulverizing with a ball mill for 100 hours. The particle diameter of the glass powder was 0.1 μm.

  From Table 2, when the content of the oxide of R1 is outside the scope of the present invention (Sample Nos. 21 and 30), the relative permittivity, capacity-temperature characteristics, high temperature load life, etc. tend to deteriorate. It could be confirmed. Further, it was confirmed that when the content of the oxide of R2 is outside the range of the present invention (sample numbers 31 and 35), the dielectric loss, the high temperature load life and the like tend to deteriorate.

  On the other hand, when the contents of the R1 and R2 oxides are within the scope of the present invention (sample numbers 22 to 29, 32 to 34), it was confirmed that good characteristics were obtained. Even when an element other than Y was selected as R1 and an element other than Dy was selected as R2 (sample numbers 24-28), it was confirmed that the same results were obtained.

  When the content of the component containing Ba and the like is out of the scope of the present invention (sample numbers 36 and 40), it was confirmed that the relative permittivity, the high temperature load life and the like tend to be deteriorated.

  On the other hand, when the content of the component is within the range of the present invention (sample numbers 37 to 39), it was confirmed that good characteristics were obtained.

  In addition, when this component was added with the form of glass powder (sample number 41), it has confirmed that there exists a tendency for a high temperature load life to deteriorate. In addition, it has been confirmed by the present inventors that when the component is added in the form of a complex oxide, the high-temperature load life tends to deteriorate as in the case of Sample No. 41.

Example 3
Except that the contents of the main component and the subcomponent are the amounts shown in Table 2 and the values of β / (α + β) and (α + β) are changed by changing the contents of the oxides of R1 and R2. In the same manner as in Example 1, a multilayer ceramic capacitor sample was prepared, and the same characteristic evaluation as in Example 1 was performed. The results are shown in Table 3.

  From Table 3, when the values of β / (α + β) and (α + β) are outside the preferred range of the present invention (sample numbers 51, 55, 56 and 60), the relative permittivity, high temperature load life, etc. tend to deteriorate. I was able to confirm.

Example 4
A multilayer ceramic capacitor sample was prepared in the same manner as Sample No. 17 in Example 1 except that the molar ratio of Ba, Ca, and Si in the component containing Ba and the like was changed to the values shown in Table 4. Example 1 The same characteristic evaluation was performed. The results are shown in Table 4.

  From Table 4, when the values of a, b and c are outside the preferred range of the present invention (sample numbers 74, 77, 78 and 81), it can be confirmed that the relative permittivity, high temperature load life, etc. tend to deteriorate. It was.

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

Claims (8)

A compound having a perovskite crystal structure represented by BaTiO ₃ as a main component;
With respect to 100 moles of the compound, in terms of each element,
0.6 to 2.0 mol of Mg oxide,
0.010 to 0.6 mol of an oxide of Mn and / or Cr,
0.010 to 0.20 mol of at least one oxide selected from the group consisting of V, Mo and W,
0.10 to 1.0 mol of an oxide of R1 (R1 is at least one selected from the group consisting of Y, Yb, Er and Ho),
0.10 to 1.0 mol of an oxide of R2 (R2 is at least one selected from the group consisting of Dy, Gd and Tb),
A dielectric ceramic composition comprising 0.2 to 1.5 moles of a component comprising Ba oxide and / or Ca oxide and Si oxide as subcomponents.   Assuming that the content of the R1 oxide in terms of R1 is α mol and the content of the R2 oxide in terms of R2 is β mol, 0.50 ≦ β / (α + β) ≦ 0.90,. The dielectric ceramic composition according to claim 1, satisfying a relationship of 2 <(α + β) <1.5. In the above-mentioned component consisting of an oxide of Ba and / or Ca and an oxide of Si, the content molar ratio of Ba is a, the content molar ratio of Ca is b, and the content molar ratio of Si is a, b and c are a + b + c = 1, a + b ≦ c, and 0 ≦ a ≦ 0.5, 0 ≦ b ≦ 0.5, and 0.5 ≦ c ≦ 0.8. The dielectric ceramic composition according to claim 1 or 2, which satisfies the relationship. The content of the R1 oxide in terms of R1 is α mol, the content of the R2 oxide in terms of R2 is β mol,
When the content in terms of each metal element of the component consisting of the oxide of Ba and / or the oxide of Ca and the oxide of Si is mmole,
The dielectric ceramic composition according to any one of claims 1 to 3, which satisfies a relationship of (α + β) /m≤10.5.   The dielectric ceramic composition according to any one of claims 1 to 4, wherein R1 is Y and R2 is Dy. The ceramic electronic component which has a dielectric material layer comprised from the dielectric material ceramic composition in any one of Claims 1-5 , and an electrode.   A method for producing the dielectric ceramic composition according to claim 1,
The component that is the raw material of the component consisting of the Ba oxide and / or Ca oxide and the Si oxide is in the form of a complex oxide of metal elements constituting the component or in the form of glass powder. Rather than adding, prepare a gel hydroxide slurry or aqueous solution of each metal element in the component,
  The gel-like hydroxide slurry or aqueous solution is used as the BaTiO. ₃ A method for producing a dielectric ceramic composition comprising the step of preparing a raw material mixture by dispersing a raw material powder and a gel-like hydroxide slurry or aqueous solution of the subcomponent metal element together with water.   The method for producing a dielectric ceramic composition according to claim 7, wherein the rare earth element as a raw material to be the oxide of R1 and the oxide of R2 is prepared as a rare earth element gel hydroxide slurry.

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