JP4770211B2 - Electronic components - Google Patents

Description

  The present invention relates to an electronic component such as a multilayer ceramic capacitor, and more particularly relates to a highly reliable electronic component having excellent IR (insulation) life and low dielectric loss in a wide temperature range.

  Multilayer ceramic capacitors as electronic components are widely used as small-sized, large-capacity, high-reliability electronic components, and the number used in one electronic device is large. In recent years, with the miniaturization and high performance of devices, the demand for further miniaturization, larger capacity, lower cost, and higher reliability for multilayer ceramic capacitors has become increasingly severe.

  Multilayer ceramic capacitors are usually laminated by a sheet method or a printing method using an internal electrode layer paste and a dielectric layer paste, and the internal electrode layer and the dielectric layer in the multilayer body are simultaneously formed. Manufactured by firing. As the conductive material for the internal electrode layer, Pd or Pd alloy is generally used. However, since Pd is expensive, a relatively inexpensive base metal such as Ni or Ni alloy has been used. When a base metal is used as the conductive material for the internal electrode layer, the internal electrode layer is oxidized when fired in the atmosphere. Therefore, it is necessary to perform simultaneous firing of the dielectric layer and the internal electrode layer in a reducing atmosphere. is there. However, when firing in a reducing atmosphere, the dielectric layer is reduced and the specific resistance is lowered. For this reason, non-reducing dielectric materials have been developed.

  However, a multilayer ceramic capacitor using a non-reducing dielectric material has a problem that IR (insulation resistance) is significantly deteriorated by application of an electric field, the IR life is short, and the reliability is low. On the other hand, for example, in the following Patent Documents 1 to 4, attempts are made to improve the reliability of the multilayer ceramic capacitor.

  In Patent Document 1, the ceramic particles constituting the dielectric layer have a core-shell structure, and the shell portion includes elements such as Mn, V, and Cr, Mg, and rare earth elements, and Mn, V, Cr, and the like. Reliability is improved by increasing the concentration of the element from the core-shell boundary toward the grain boundary. In Patent Document 2, the ceramic particles constituting the dielectric layer have a core-shell structure, and the core part contains elements such as Mn, V, and Cr with a concentration gradient, thereby improving reliability. I am trying.

  In Patent Document 3, the ceramic particles constituting the dielectric layer are solid solutions containing elements such as Mn, V, Cr, and rare earth elements, and the concentration of these elements is directed from the center of the ceramic particles to the grain boundary. Therefore, the reliability is improved. In Patent Document 4, the dielectric layer is composed of ceramic particles and vitreous grain boundary parts that connect and coat the ceramic particles, and the grain boundary part contains elements such as Mn, V, Cr, etc. The improvement of the nature is aimed at.

  However, in these Patent Documents 1 to 4, the specific content ratio of elements such as Mn, V, Cr, etc. in the ceramic particles (and the grain boundary part) is not described at all, and any ratio may be used. It is unclear whether the effects described in each document can be obtained. Moreover, in these literatures, since the relatively expensive rare earth element was added, there also existed a problem that cost increased. In each of these documents, the reoxidation treatment (annealing) is performed at a relatively low temperature (600 ° C.).

  On the other hand, the capacitor is also required to have good temperature characteristics. In particular, depending on the application, the temperature characteristics are required to be flat under severe conditions. In recent years, multilayer ceramic capacitors have been used in various electronic devices such as an engine electronic control unit (ECU), a crank angle sensor, and an antilock brake system (ABS) module mounted in an engine room of an automobile. Since these electronic devices are for performing engine control, drive control and brake control stably, it is required that the circuit has good temperature stability.

  The environment in which these electronic devices are used is expected to decrease to about −20 ° C. or lower in winter in cold regions, and to increase to about + 130 ° C. or higher in summer after engine startup. Recently, there is a tendency to reduce the number of wire harnesses that connect an electronic device and its control target equipment, and the electronic device is sometimes installed outside the vehicle, so the environment for the electronic device has become increasingly severe. Therefore, capacitors used in these electronic devices need to have flat temperature characteristics over a wide temperature range.

However, in the above-mentioned Patent Documents 1 to 4, since none of them aims at temperature compensation, there is a problem that the electrical characteristics at a low temperature or at a high temperature are inferior. In order to solve such a problem, for example, Patent Document 5 discloses a (Ca, Me) (Zr, Ti) O ₃ system (where Me is Sr, Mg) as a temperature compensation capacitor having excellent temperature characteristics. And a capacitor having a dielectric layer containing at least one main component of Ba and Mn and Mn. However, the capacitor described in this document has a problem that it is inferior in IR life and dielectric loss, although it is excellent in the temperature characteristic of capacitance.

JP 2001-230149 A JP 2001-230150 A JP 2001-230148 A JP 2001-307939 A JP 2004-262680 A

  The present invention has been made in view of such a situation, and is excellent in IR life and maintains a wide temperature range (for example, −55 to 155 ° C.) while maintaining various electrical characteristics such as dielectric constant and temperature characteristics of capacitance. It is an object of the present invention to provide a highly reliable electronic component such as a monolithic ceramic capacitor that can keep dielectric loss low.

In order to achieve the above object, an electronic component according to the present invention includes:
An electronic component having a dielectric layer,
The dielectric layer contains at least Mn element, and
A plurality of ceramic particles, and a crystal grain boundary existing between the adjacent ceramic particles,
Content ratio (α) of Mn element in the ceramic particles with respect to all elements constituting the dielectric layer, and content ratio (β) of Mn element in the crystal grain boundary with respect to all elements constituting the dielectric layer The Mn element ratio (β / α), which is a ratio of the above, is greater than 1 and equal to or less than 3.1.

  In the present invention, by setting the Mn element ratio (β / α) within the predetermined range, the IR life can be improved, and the dielectric loss can be kept low over a wide temperature range, so that the reliability is high. An electronic component can be obtained.

  In the present invention, the content ratio (α) of the Mn element in the ceramic particles is a weight ratio (unit:% by weight) of the Mn element to the content of 100% by weight of all elements constituting the entire dielectric layer. The mean value of the weight ratio of the Mn element in the entire ceramic particle is meant. That is, in the present invention, the content ratio (α) of the Mn element in the ceramic particles is an average value of the content ratio of the Mn element not only in the vicinity of the surface of the ceramic particles but also in all the portions including the central portion.

  Similarly, the content ratio (β) of the Mn element in the crystal grain boundary is the weight ratio of the Mn element to the content of 100% by weight of all the elements constituting the entire dielectric layer (unit is weight%). It means the content ratio of Mn element in the vicinity of the ceramic particles in the grain boundary.

In the electronic component of the present invention, preferably,
The dielectric layer includes a dielectric ceramic composition;
The dielectric ceramic composition is represented by a composition formula {(Ca _1−x Me _x ) O} _m · (Zr _1−y Ti _y ) O ₂ , and a symbol Me indicating an element name in the composition formula is: The symbols m, x, and y, which are at least one of Sr, Mg, and Ba and indicate the composition molar ratio, are 0.8 ≦ m ≦ 1.3, 0 ≦ x ≦ 1.00, and 0 ≦ y ≦ 0.8. A main component containing a dielectric oxide in the relationship of
A third subcomponent containing an oxide of Mn,
The ratio of the third subcomponent to 100 mol of the main component is 0 mol <third subcomponent <5 mol in terms of Mn element in the oxide of Mn.

  In the present invention, by making the dielectric ceramic composition contained in the dielectric layer within the above composition range, the temperature dependence of the capacitance can be lowered, and it is suitable as an electronic component for temperature compensation. Can be used.

In the electronic component of the present invention, preferably,
The dielectric ceramic composition is
A first subcomponent comprising an oxide of V;
A second subcomponent containing an oxide of Al,
The ratio of each component to 100 moles of the main component is
First subcomponent: 0 mole <first subcomponent <7 moles (note _that the value in terms of V 2 _{O 5),}
Second subcomponent: 0 mol <second subcomponent <15 mol (however, converted to Al ₂ O ₃ ).

In the electronic component of the present invention, preferably,
The dielectric ceramic composition is
The SiO ₂ as a main component, MO (provided that, M is at least one element selected from Ba, Ca, Sr and Mg), fourth sub comprises at least one selected from Li ₂ O and _B 2 _{O 3} Further containing ingredients,
The ratio of the fourth subcomponent to 100 mol of the main component is 0 mol <fourth subcomponent <20 mol in terms of oxide.

  In the present invention, in addition to the main component and the third subcomponent, preferably, the first subcomponent and the second subcomponent, more preferably the fourth subcomponent, further includes a capacitance temperature. Dependency can be further improved.

More preferably, the fourth subcomponent is represented by a compositional formula {(Ba _z , Ca _1−z ) O} _v SiO ₂ , and symbols z and v indicating a composition molar ratio in the compositional formula are 0 ≦ A composite oxide having a relationship of z ≦ 1 and 0.5 ≦ v ≦ 4.0 is included.

An electronic component manufacturing method according to the present invention includes:
A method of manufacturing an electronic component having a dielectric layer,
Dielectric porcelain composition material containing a third subcomponent material containing an oxide of Mn and / or a compound that becomes an oxide of Mn after firing as a dielectric porcelain composition material that constitutes the dielectric layer And
The sintered body after firing has a step of subjecting to re-oxidation treatment at a temperature higher than 900 ° C. and lower than 1150 ° C.

In the manufacturing method of this invention, it is preferable that the oxygen partial pressure of the said reoxidation process shall be 4.1 * 10 < ^-9 > -6.9 * 10 < ^-7 > MPa. The reoxidation treatment time is preferably 2 to 6 hours.

  In the production method of the present invention, the reoxidation treatment is performed at the above temperature (preferably, the oxygen partial pressure and the time), so that the Mn element in the ceramic particle particles constituting the dielectric layer is formed. The Mn element ratio (β / α), which is the ratio of the content ratio (α) and the content ratio (β) of the Mn element at the crystal grain boundary, can be controlled to a desired ratio.

In the production method of the present invention, preferably, the dielectric ceramic composition raw material is represented by a composition formula {(Ca _1−x Me _x ) O} _m · (Zr _1−y Ti _y ) O ₂ , and the composition The symbol Me indicating the element name in the formula is at least one of Sr, Mg and Ba, and the symbols m, x and y indicating the composition molar ratio are 0.8 ≦ m ≦ 1.3, 0 ≦ x ≦ A main component material containing a dielectric oxide having a relationship of 1.00 and 0 ≦ y ≦ 0.8 is further contained.

  In the production method of the present invention, preferably, the ratio of the third subcomponent raw material to 100 mol of the main component raw material is 0 mol <third subcomponent raw material <5 mol in terms of Mn element.

In the production method of the present invention, preferably, the dielectric ceramic composition raw material includes a first subcomponent raw material containing a V oxide and / or a compound that becomes a V oxide after firing, an Al oxide and / or Or a second subcomponent material containing a compound that becomes an oxide of Al by firing, and the ratio of each subcomponent material to 100 mol of the main component material is such that the first subcomponent material: 0 mol <first Subcomponent raw material <7 mol (however, converted to V ₂ O ₅ ), second subcomponent raw material: 0 mol <second subcomponent raw material <15 mol (however, converted to Al ₂ O ₃ ) .

In the production method of the present invention, more preferably, the dielectric ceramic composition raw material is converted to SiO ₂ , BaO, CaO, SrO, MgO, Li ₂ O, B ₂ O ₃ , and / or these oxides by firing. A fourth subcomponent raw material containing at least one selected from the following compounds, and the ratio of the fourth subcomponent raw material to 100 mol of the main component is 0 mol <fourth subcomponent raw material < 20 moles.

  In the present invention, the electronic component is not particularly limited, and examples thereof include a multilayer ceramic capacitor, a piezoelectric element, a chip inductor, a chip varistor, a chip thermistor, a chip resistor, and other surface mount (SMD) chip type electronic components.

  According to the present invention, the Mn element ratio (ratio) of the content ratio (α) of Mn element in the ceramic particles constituting the dielectric layer and the content ratio (β) of Mn element in the crystal grain boundary ( By controlling β / α to a predetermined range, while maintaining various electrical characteristics such as dielectric constant and capacitance temperature characteristics, the IR life is excellent and a wide temperature range (for example, −55 to 155 ° C.). Range), an electronic component such as a multilayer ceramic capacitor having a low dielectric loss can be provided.

Hereinafter, the present invention will be described based on embodiments shown in the drawings.
FIG. 1 is a cross-sectional view of a multilayer ceramic capacitor according to an embodiment of the present invention.
FIG. 2 is an enlarged cross-sectional view of a dielectric layer of a multilayer ceramic capacitor according to an embodiment of the present invention,
FIG. 3 is a diagram for explaining a method for measuring the Mn element ratio (β / α) in the present invention;
FIG. 4 is a graph showing the relationship of the Mn content in the grains and at the grain boundaries of the multilayer ceramic capacitor according to the example of the present invention,
FIG. 5 is a graph showing the relationship between the measured temperature and the dielectric loss of the multilayer ceramic capacitor according to the example of the present invention.

Multilayer ceramic capacitor 1
As shown in FIG. 1, a multilayer ceramic capacitor 1 as an electronic component according to an embodiment of the present invention includes a capacitor element body 10 in which dielectric layers 2 and internal electrode layers 3 are alternately stacked. At both ends of the capacitor element body 10, a pair of external electrodes 4 are formed which are electrically connected to the internal electrode layers 3 arranged alternately in the element body 10. The 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 outer shape and dimensions of the capacitor element body 10 are not particularly limited and can be appropriately set according to the application. Usually, the outer shape is substantially a rectangular parallelepiped shape, and the dimensions are vertical (0.4 to 5.6 mm) × horizontal. (0.2 to 5.0 mm) × height (0.2 to 1.9 mm).

Dielectric layer 2
The dielectric layer 2 includes a main component including a dielectric oxide represented by a composition formula {(Ca _1−x Me _x ) O} _m · (Zr _1−y Ti _y ) O ₂ and an oxide of Mn. It is preferable to be comprised from the dielectric ceramic composition containing a 3rd subcomponent. In the above formula, the amount of oxygen (O) may be slightly deviated from the stoichiometric composition of the above formula.

  In the above formula, x is preferably 0 ≦ x ≦ 1.00. x represents the number of atoms of the symbol Me (where Me is at least one of Sr, Mg, and Ba, among which Sr is preferable), and the phase transition point of the crystal can be arbitrarily determined by changing x, that is, the symbol Me / Ca ratio. Can be shifted to. Therefore, the capacity temperature coefficient and the relative dielectric constant can be arbitrarily controlled. However, in the present invention, the ratio between Ca and the symbol Me is arbitrary, and only one of them may be contained.

In the above formula, y is preferably 0 ≦ y ≦ 0.8. Although y represents the number of Ti atoms, there is a tendency that the reduction resistance is further increased by substituting ZrO ₂ which is not easily reduced as compared with TiO ₂ .

  In the above formula, m is preferably 0.8 ≦ m ≦ 1.3, more preferably 0.970 ≦ m ≦ 1.030. By making m 0.8 or more, it is possible to prevent the formation of a semiconductor for firing in a reducing atmosphere, and by making m 1.3 or less, dense sintering can be achieved without increasing the firing temperature. You can get a body.

  The third subcomponent has an effect of promoting sintering, an effect of imparting reduction resistance to the dielectric layer, and further functions as an acceptor. The ratio of the third subcomponent to 100 mol of the main component is preferably 0 mol <third subcomponent <5 mol, more preferably 0.1 mol ≦ third subcomponent ≦ 4 mol in terms of Mn element in the oxide. And If the amount of the third subcomponent added is too large, the IR life tends to be reduced. In addition, at least a part of the third subcomponent may be segregated in a discontinuous portion of the internal electrode layer 3 or the like.

In the present embodiment, the dielectric ceramic composition constituting the dielectric layer 2 is
A first subcomponent comprising an oxide of V;
It is preferable to further contain a second subcomponent containing an oxide of Al.
By containing a predetermined amount of the first subcomponent and the second subcomponent, low-temperature firing is possible without deteriorating the dielectric characteristics, and the IR life is improved even when the dielectric layer 2 is thinned. Can do.

The ratio of the first subcomponent to 100 mol of the main component is preferably 0 mol <first subcomponent <7 mol, more preferably 0.01 mol ≦ first subcomponent ≦ 5 mol in terms of V ₂ O _5. .
The ratio of the second subcomponent to 100 mol of the main component is preferably 0 mol <second subcomponent <15 mol, more preferably 0.01 mol ≦ second subcomponent ≦ 10 mol in terms of Al ₂ O _3. .
By setting the ratio of the first subcomponent and the second subcomponent in the above range, the IR life can be improved when y is in the range of 0 ≦ y ≦ 0.8. A part of the oxide of V contained in the first subcomponent may be replaced with an oxide of a Group 5 element such as Nb or Ta or an oxide of a Group 6 element of Cr, Mo, or W. .

In the present embodiment, the dielectric ceramic composition constituting the dielectric layer 2 contains SiO ₂ as a main component in addition to the main component and the first to third subcomponents, and MO (where M is Ba , At least one element selected from Ca, Sr and Mg), and a fourth subcomponent containing at least one selected from Li ₂ O and B ₂ O ₃ . This fourth subcomponent mainly acts as a sintering aid, but also has an effect of improving the defective rate of the initial insulation resistance (IR) when the dielectric layer 2 is thinned.

Preferably, the fourth subcomponent includes a composition formula _{{(Ba z, Ca 1-} z) O} v composite oxide represented by SiO ₂ (hereinafter, sometimes also referred to as BCG). A composite oxide _{{(Ba z, Ca 1-} z) O} v SiO 2 has a low melting point, has a good reactivity with the main component. In the composition formula {(Ba _z , Ca _1−z ) O} _v SiO ₂ , the symbol v indicating the composition molar ratio in the composition formula is preferably 0.5 ≦ v ≦ 4.0, more preferably 0. .5 ≦ v ≦ 2.0. If v is too small, that is, if SiO ₂ is too much, it reacts with the main component and deteriorates the dielectric properties. On the other hand, if v is too large, the melting point of the composite oxide becomes high and the sinterability of the dielectric layer is deteriorated. The symbol z indicating the composition molar ratio of Ba and Ca is arbitrary (0 ≦ z ≦ 1) and may contain only one, but preferably 0.3 ≦ z ≦ 0.7. It is.

  The ratio of the fourth subcomponent to 100 mol of the main component is preferably 0 mol <4 subcomponent <20 mol, more preferably 0.1 mol ≦ fourth subcomponent, in terms of oxide (or composite oxide). ≦ 15 mol. Adding a small amount of the fourth subcomponent is effective in reducing the occurrence of the initial IR defect rate, and by making the addition amount less than 20 moles, the reduction in the relative dielectric constant is suppressed and sufficient capacity is obtained. Can be secured.

  As shown in FIG. 2, the dielectric layer 2 includes ceramic particles 21 and crystal grain boundaries 22 formed between adjacent ceramic particles 21. In the present embodiment, the ratio of the content ratio (α) of the Mn element in the particles of the ceramic particles 21 (hereinafter, appropriately referred to as the grains) and the content ratio (β) of the Mn element in the crystal grain boundary 22 is a ratio. The Mn element ratio (β / α) is larger than 1 and 3.1 or less, preferably 1.3 or more and 2.4 or less. In the present embodiment, the content ratios (α) and (β) of the Mn element are both weight ratios (unit: weight%) with respect to 100% by weight of all elements constituting the entire dielectric layer 2.

  The present invention is characterized in that the Mn element ratio (β / α) is in the above predetermined range, and the IR life is improved by configuring the ceramic particles 21 and the crystal grain boundaries 22 in such a configuration. In addition, the dielectric loss can be kept low over a wide temperature range. If the Mn element ratio (β / α) is too large, the effects of the present invention, that is, the IR lifetime and dielectric loss improvement effects cannot be obtained. Further, the Mn element ratio (β / α) is difficult to be 1 or less for the following reason. That is, it is possible to reduce the Mn element ratio (β / α) by lengthening the reoxidation treatment time, but it takes a very long time to make it 1 or less, When the re-oxidation treatment is performed for a long time, the internal electrode is remarkably oxidized, which causes a problem of insufficient capacity.

In addition, it does not specifically limit as a method of measuring Mn element ratio ((beta) / (alpha)), For example, it can measure with the following method.
First, the element body 10 is cut in a direction perpendicular to the dielectric layer 2. And in this cut surface, the content ratio (α) of the Mn element in the grains of the ceramic particles 21 and the content ratio (β) of the Mn element in the crystal grain boundaries 22 are measured by a transmission electron microscope (TEM). The Mn element ratio (β / α) is calculated from the obtained measurement result. When measuring the content ratio (α) of the Mn element in the grains of the ceramic particles 21, the content ratio of the Mn element at a plurality of points on a straight line passing through the approximate center of the ceramic particles 21 is measured, and the measurement result is obtained. On average, the content is (α). Further, the content ratio (β) of the Mn element in the crystal grain boundary 22 is obtained by measuring the content ratio of the Mn element in the vicinity of the ceramic particles 21 in the crystal grain boundary 22 and setting the result as the content ratio (β). The content ratio (β) is preferably the content ratio (β) obtained by measuring the content ratio of two or more places in the vicinity of the ceramic particles 21 and averaging the measurement results.

  The thickness of the dielectric layer 2 is not particularly limited, but is preferably 1 μm or more and 100 μm or less per layer, and more preferably 2 μm or more and 20 μm or less. If the dielectric layer is too thin, insulation failure tends to occur. Moreover, since it will become easy to generate | occur | produce a sheet | seat defect when it is too thick, it becomes easy to generate | occur | produce an insulation defect similarly.

  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 base metal can be used because the constituent material of the dielectric layer 2 has reduction resistance. As the base metal used as the conductive material, Ni or Ni alloy is preferable. The Ni alloy is preferably an alloy of Ni and one or more elements selected from Mn, Cr, Co and Al, and the Ni content in the alloy is preferably 95% by weight or more. In addition, in Ni or Ni alloy, various trace components, such as P, may be contained about 0.1 wt% or less.

  The thickness of the internal electrode layer 3 is preferably 3 μm or less, more preferably 0.5 μm or more and 2.5 μm or less. If the internal electrode layer 3 is too thick, it is difficult to reduce the size of the capacitor. On the other hand, when the internal electrode layer 3 is too thin, there is a tendency that the electrode interruption due to the spheroidization of the electrode or the like occurs remarkably.

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 may be appropriately determined according to the use, etc., 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, a dielectric ceramic composition powder contained in the dielectric layer paste is prepared.
In producing the dielectric layer paste, first, a dielectric ceramic composition raw material contained therein is prepared. The dielectric ceramic composition material includes a main component material and first to fourth subcomponent materials. In addition, what is necessary is just to prepare the mixing ratio of each raw material contained in a dielectric ceramic composition raw material so that the ratio after baking may become the above-mentioned predetermined ratio.

As the main component raw material, a raw material represented by a composition formula {(Ca _1−x Me _x ) O} _m · (Zr _1−y Ti _y ) O ₂ is used. The main component material may be obtained by a so-called liquid phase method in addition to a so-called solid phase method. In the solid phase method, for example, when SrCO ₃ , CaCO ₃ , TiO ₂ , and ZrO ₂ are used as starting materials, a predetermined amount is weighed, mixed, calcined, and pulverized to obtain a raw material. Examples of the liquid phase synthesis method include an oxalate method, a hydrothermal synthesis method, and a sol-gel method.

As the first subcomponent material, a V oxide and / or a compound that becomes a V oxide after firing is used. As the second subcomponent raw material, an Al oxide and / or a compound that becomes an Al oxide by firing is used. As the third subcomponent material, an oxide of Mn and / or a compound that becomes an oxide of Mn by firing is used. As the fourth subcomponent material, SiO ₂ , BaO, CaO, SrO, MgO, Li ₂ O, B ₂ O ₃ , and / or compounds that become these oxides by firing are used.

  The method for producing the dielectric ceramic composition raw material is not particularly limited. For example, when the main component raw material is produced, subcomponent raw materials such as the first to fourth subcomponent raw materials are mixed with the starting raw material, The dielectric ceramic composition material may be obtained simultaneously with the production of the main component material by the phase method or the liquid phase method. Alternatively, once the main component material is manufactured by a solid phase method, a liquid phase method, or the like, and a subcomponent material such as the first to fourth subcomponent materials is added thereto, the dielectric ceramic composition material is obtained. You may get.

  Hereinafter, a method of obtaining a dielectric ceramic composition raw material by mixing the first to fourth subcomponent raw materials when producing the main component raw material by the solid phase method will be described as an example.

First, for example, in addition to SrCO _3, CaCO _3, the starting materials of the main component material, such as _TiO 2, ZrO _2, at least a portion of the first subcomponent material to the final composition (e.g. _V 2 _O 5), second sub By weighing, mixing, and drying component raw materials (for example, Al ₂ O ₃ ), third sub-component raw materials (for example, MnCO ₃ ), and fourth sub-component raw materials (for example, (Ba, Ca) _z SiO _{2 + z} ) Prepare raw materials before calcining.

  Next, the prepared pre-calcination powder is calcined to obtain a calcined powder. The calcining conditions are not particularly limited, but are preferably performed under the following conditions. The rate of temperature rise is preferably 50 to 400 ° C./hour, more preferably 100 to 300 ° C./hour. The holding temperature is preferably 1000 to 1300 ° C. The temperature holding time is preferably 0.5 to 6 hours, more preferably 1 to 3 hours. The treatment atmosphere may be any of air, nitrogen, and reducing atmosphere.

  The obtained calcined powder is coarsely pulverized with an alumina roll or the like, and if necessary, the remaining additives (including the remainder of the first to fourth subcomponent raw materials) are added to the final composition. To do. Thereafter, the mixed powder is mixed by a ball mill or the like, if necessary, and dried to obtain a dielectric ceramic composition raw material (powder).

In addition, as the dielectric ceramic composition raw material, the above-described oxide, a mixture thereof, or a composite oxide can be used. In addition, various compounds that become the above-described oxide or composite oxide by firing, for example, carbonates , Oxalates, nitrates, hydroxides, organometallic compounds, and the like may be selected as appropriate and used as a mixture. What is necessary is just to determine content of each compound in a dielectric ceramic composition raw material so that it may become a composition of the above-mentioned dielectric ceramic composition after baking.
The particle size of the dielectric ceramic composition powder is usually about 0.1 to 3 μm in average particle size in a state before being formed into a paint.

  Next, the dielectric ceramic composition raw 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 ceramic composition 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. Further, the organic solvent to be used is not particularly limited, and may be appropriately selected from various organic solvents such as terpineol, butyl carbitol, acetone, toluene, and the like, depending on a method to be used such as a printing method or a sheet method.

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

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

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

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

Before firing, the green chip is subjected to binder removal processing. The binder removal treatment 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 in the binder removal atmosphere is 10 It is preferable to be ⁻⁴⁵ to 10 ⁵ Pa. When the oxygen partial pressure is less than the above range, the binder removal effect is lowered. If the oxygen partial pressure exceeds the above range, the internal electrode layer tends to oxidize.

As other binder removal conditions, the temperature rising rate is preferably 5 to 300 ° C./hour, more preferably 10 to 100 ° C./hour, and the holding temperature is preferably 180 to 400 ° C., more preferably 200 to 350. The temperature holding time is preferably 0.5 to 24 hours, more preferably 2 to 20 hours. The firing atmosphere is preferably air or a reducing atmosphere, and as an atmosphere gas in the reducing atmosphere, for example, a mixed gas of N ₂ and H ₂ is preferably used after being humidified.

The atmosphere at the time of green chip firing may be appropriately determined according to the type of conductive material in the internal electrode layer paste, but when a base metal such as Ni or Ni alloy is used as the conductive material, the oxygen content in the firing atmosphere The pressure is preferably 10 ⁻¹³ to 10 ⁻⁹ 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.

  Moreover, the holding temperature at the time of baking becomes like this. Preferably it is 1100-1400 degreeC, More preferably, it is 1200-1380 degreeC, More preferably, it is 1260-1360 degreeC. If the holding temperature is lower than the above range, the densification becomes insufficient. If the holding temperature is higher than the above range, abnormal sintering of the internal electrode layer, deterioration of capacity temperature characteristics due to diffusion of the constituent material of the internal electrode layer, dielectric ceramic composition The reduction of is likely to occur.

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

  Next, the capacitor element body is subjected to reoxidation treatment (annealing). The re-oxidation process is a process for re-oxidizing the dielectric layer, and as a result, the IR life can be remarkably increased, so that the reliability is improved.

  The holding temperature (reoxidation temperature) during the reoxidation treatment is preferably higher than 900 ° C. and lower than 1150 ° C., more preferably 1000 ° C. or higher and 1100 ° C. or lower. In the present embodiment, by setting the holding temperature of the reoxidation treatment in the above range, the content ratio (α) of Mn element in the grains of the ceramic particles 21 constituting the dielectric layer 2 and the grain boundary It is possible to control the Mn element ratio (β / α), which is the ratio of the Mn element content ratio (β) in 22, to a desired ratio.

  If the holding temperature is too low, the Mn element ratio (β / α) becomes too large, and it becomes difficult to obtain the effects of the present invention. On the other hand, if the holding temperature is too high, not only does the capacity decrease due to oxidation of the internal electrode layer 3, but the internal electrode layer 3 reacts with the dielectric substrate, resulting in deterioration of the capacity-temperature characteristics, IR reduction, IR lifetime. Is likely to occur.

The oxygen partial pressure during the re-oxidation treatment is preferably 4.1 × 10 ^{−9 to} 6.9 × 10 ⁻⁷ MPa, more preferably 7.6 × 10 ^{−8 to} 4.2 × 10 ⁻⁷ MPa. To do. If the oxygen partial pressure is too low, reoxidation tends to be insufficient. On the other hand, if the oxygen partial pressure is too high, the internal electrode layer 3 is oxidized. Note that the oxygen partial pressure may be adjusted using, for example, humidified N ₂ gas or the like as the re-oxidation atmosphere gas.

  Moreover, the temperature holding time (reoxidation time) during the reoxidation treatment is preferably 2 to 6 hours, more preferably 2 to 3 hours. In this embodiment, since the reoxidation process is performed at a relatively high temperature, the effect of the reoxidation process can be sufficiently obtained even when the temperature holding time is relatively short. If the temperature holding time is too long, the internal electrode is oxidized. In addition, when the holding time is long, there is a problem that productivity is lowered. As re-oxidation treatment conditions other than the above, the cooling rate is preferably 50 to 500 ° C./hour, more preferably 100 to 300 ° C./hour.

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

The binder removal treatment, firing and reoxidation treatment may be performed continuously or independently. When these are performed continuously, after removing the binder, the atmosphere is changed without cooling, and then the temperature is raised to the holding temperature at the time of baking to perform baking, and then cooled to the holding temperature for the reoxidation treatment. When it reaches, it is preferable to perform reoxidation treatment by changing the atmosphere. On the other hand, when performing these independently, at the time of firing, after raising the temperature under N ₂ gas atmosphere with N ₂ gas or wet to the holding temperature of the binder removal processing, further continuing the heating to change the atmosphere Preferably, after cooling to the holding temperature at the time of re-oxidation, it is preferable to change to N ₂ gas or a humidified N ₂ gas atmosphere again and continue cooling. In the re-oxidation treatment, the temperature may be changed to a holding temperature in an N ₂ gas atmosphere, and then the atmosphere may be changed, or the entire process of the re-oxidation treatment may be a humidified N ₂ gas atmosphere.

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

  In the present embodiment, the ratio of the content ratio (α) of Mn element in the ceramic particles 21 forming the dielectric layer 2 to the content ratio (β) of Mn element in the crystal grain boundary 22 A certain Mn element ratio (β / α) is set to be larger than 1 and 3.1 or less. Therefore, the IR life can be improved and the dielectric loss can be lowered in a wide temperature range (for example, a range of −55 to 150 ° C.). In particular, by suppressing the dielectric loss low in a wide temperature range, deterioration of the dielectric layer 2 due to heat generation under an AC voltage can be suppressed.

  Furthermore, in the present embodiment, the dielectric layer 2 contains the above-described oxides (composite oxides) as the main component and the first to fourth subcomponents. Therefore, the temperature dependence of the capacitance can be reduced, and the capacitance can be suitably used as a multilayer ceramic capacitor for temperature compensation.

  As mentioned above, although embodiment of this invention has been described, this invention is not limited to the embodiment mentioned above at all, and can be variously modified within the range which does not deviate from the summary of this invention. For example, in the above-described embodiment, the multilayer ceramic capacitor is exemplified as the multilayer ceramic electronic component according to the present invention. However, the electronic component according to the present invention is not limited to the multilayer ceramic capacitor and has the predetermined configuration of the present invention. Anything can be used.

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

Example 1
First, as starting materials for producing a dielectric material, main component materials (SrCO ₃ , CaCO ₃ , TiO ₂ , ZrO ₂ ) and first to fourth subcomponent materials having an average particle diameter of 0.1 to 1 μm are used. Prepared. In this embodiment, carbonate (third subcomponent: MnCO ₃ ) is used as the raw material for MnO, and oxides (first subcomponent: V ₂ O ₅ , second subcomponent: Al ₂ O) are used as the other raw materials. ₃ , 4th subcomponent: (Ba _0.6 Ca _0.4 ) SiO ₃ was used, and (Ba _0.6 Ca _0.4 ) SiO ₃ was obtained by ball milling BaCO ₃ , CaCO ₃ and SiO ₂ with a ball mill. The mixture was wet-mixed for 16 hours, dried, fired in air at 1000 to 1300 ° C., and further wet-ground by a ball mill for 100 hours.

Next, the main component material and the first to fourth subcomponent materials have a composition of the main component after firing of (Ca _0.6 Sr _0.4 ) _0.995 · (Zr _0.78 Ti _0.22 ) O ₃ , first to fourth subcomponents were weighed and mixed so as to have the following blending ratio, and dried to prepare a pre-calcination powder.
V ₂ O ₅ (first subcomponent): 0.1 mol Al ₂ O ₃ (second subcomponent): 0.4 mol MnCO ₃ (third subcomponent): 1 mol (Ba _0.6 Ca _0.4 ) SiO ₃ (fourth subcomponent): 2 moles Note that the blending ratio of each of the above subcomponents is a blending ratio with respect to 100 moles of the main component, and the first subcomponent and the second subcomponent are blending ratios of each oxide The third subcomponent is a compounding ratio in terms of Mn element, and the fourth subcomponent is a compounding ratio in terms of complex oxide.

  Next, this pre-calcined powder was calcined. The calcining conditions were temperature rising rate: 300 ° C./hour, holding temperature: 1000 to 1300 ° C., temperature holding time: 2 hours, and atmosphere: in the air. Next, the material obtained by calcining was pulverized with an alumina roll to obtain calcined powder (dielectric ceramic composition raw material).

  The dielectric ceramic composition raw material thus obtained was mixed with an acrylic resin, ethyl acetate, mineral spirit and acetone with a ball mill to obtain a paste for a dielectric layer.

  The internal electrode layer paste was manufactured by kneading Ni particles having an average particle size of 0.1 to 0.8 μm, an organic vehicle, and butyl carbitol with three rolls to form a paste.

  The external electrode paste was produced by kneading Cu particles having an average particle diameter of 0.5 μm, an organic vehicle, and butyl carbitol into a paste.

  Next, a green sheet was formed on the PET film using the dielectric layer paste, the internal electrode layer paste was printed thereon, and then the green sheet was peeled from the PET film. Then, these green sheets and protective green sheets (not printed with the internal electrode layer paste) were laminated and pressure-bonded to obtain green chips. The number of sheets having internal electrodes was 10 layers.

Next, the green chip was cut into a predetermined size, subjected to binder removal processing and firing, to obtain a sintered body.
The binder removal treatment was performed under conditions of a temperature rising time of 15 ° C./hour, a holding temperature of 280 ° C., a holding time of 8 hours, and an air atmosphere.
Firing is performed at a heating rate of 200 ° C./hour, a holding temperature of 1250 to 1350 ° C., a holding time of 2 to 3 hours, a cooling rate of 300 ° C./hour, and a humidified N ₂ + H ₂ mixed gas atmosphere (oxygen partial pressure is 2 × 10 ^{−13 to} 5 × 10 ⁻¹⁰ MPa). Note that a wetter was used for humidifying the atmospheric gas during firing.

Next, the sintered body obtained above was subjected to reoxidation treatment (annealing). In this example, reoxidation treatment was performed under the conditions shown in Table 1, and samples Nos. 1 to 9 were obtained. Samples 1, 3, 4, 5, 7 and 9 were reoxidized in an N ₂ gas atmosphere humidified by a wetter with a water temperature of 35 ° C. Sample 8 is a sample that was not subjected to reoxidation treatment.

Next, after polishing the end face of the obtained sintered body by sand blasting, the external electrode paste is transferred to the end face and baked at 800 ° C. for 10 minutes in a humidified N ₂ + H ₂ atmosphere. A multilayer ceramic capacitor sample having the structure shown in FIG. 1 was obtained. The size of each sample thus obtained is 3.2 mm × 1.6 mm × 0.6 mm, the number of dielectric layers sandwiched between internal electrode layers is 10, and the thickness is 6 μm. The thickness of the internal electrode layer was 1.5 μm. The following characteristics were evaluated for each sample.

Mn element ratio (β / α)
The Mn element ratio (ratio of the Mn element content ratio (α) in the grains of the ceramic particles forming the dielectric layer of each capacitor sample and the Mn element content ratio (β) in the crystal grain boundary ( β / α) was measured by the following method.
First, the capacitor sample was cut in a direction perpendicular to the dielectric layer 2. And about this cut surface, the content rate of the Mn element in each measurement point shown in FIG. 3 (TEM image of a dielectric material layer) was measured with the transmission electron microscope (TEM). In addition, each measurement point shown in FIG. 3 is a total of 10 points, and is a point arranged in a line at equal intervals on the straight line passing through the approximate center of the ceramic particles. At each measurement point, the Mn element content in the crystal grain boundary can be measured at the measurement points at both ends (measurement points 1 and 10), and at other measurement points (measurement points 2 to 9), ceramic particles can be measured. The content ratio of the Mn element can be measured. In FIG. 3, measurement points 2 to 9 are in the order of measurement point 2, measurement point 3,..., Measurement point 9 from the measurement point 1 side.

  And the content rate ((alpha)) of the Mn element in a grain was computed by calculating the average value of the content rate of the Mn element measured at the measurement points 2-9. Furthermore, the content ratio (β) of the Mn element at the crystal grain boundary was calculated by calculating the average value of the content ratio of the Mn element measured at the measurement points 1 and 10. Finally, the Mn element ratio (β / α) was determined by dividing the content ratio (β) of the Mn element in the crystal grain boundary by the content ratio (α) of the Mn element in the grain. The results are shown in Table 1. FIG. 4 is a graph showing the content of MnO (in terms of Mn element) at the measurement points 1 to 10 of samples 1, 4, 6, and 8. In this example, the content ratios (α) and (β) of the Mn element were set to a weight ratio (unit:% by weight) with respect to the content of 100% by weight for all elements constituting the dielectric layer.

IR life For each capacitor sample, the IR life was measured by maintaining a DC voltage of 100 V / μm at 200 ° C. This IR life was evaluated by measuring 10 life samples and measuring the average life time. In this example, the time from the start of application until the resistance drops by an order of magnitude was defined as the lifetime. The results are shown in Table 1.

Dielectric loss (tan δ)
For each capacitor sample, dielectric loss (tan δ) under the conditions of a measurement temperature of −55 ° C. to + 155 ° C. with a digital LCR meter (YHP 4274A) at a frequency of 1 kHz and an input signal level (measurement voltage) of 1 Vrms. The unit is%). The results are shown in FIG. Table 1 shows the measurement results at 25 ° C. and 155 ° C.

Dielectric constant (ε)
The capacitance of each capacitor sample was measured with a digital LCR meter (4274A manufactured by YHP) at a reference temperature of 25 ° C. under conditions of a frequency of 1 kHz and an input signal level (measurement voltage) of 1 Vrms. Then, the relative dielectric constant (ε, no unit) was calculated from the obtained capacitance, the electrode dimensions of the capacitor sample, and the distance between the electrodes. As a result, good results were obtained for all samples of 56 or more.

Temperature characteristics of capacitance For each capacitor sample, the capacitance at 1 kHz and 1 V was measured using an LCR meter, and the reference temperature was 20 ° C. Whether the capacitance change rate with respect to temperature satisfies −3000 to 0 ppm / ° C. was examined. As a result, it was confirmed that all samples were satisfied.

Table 1 shows the measurement results of the reoxidation treatment conditions, Mn element ratio (β / α), IR lifetime, and dielectric loss of Samples 1-9.
From Table 1, in Samples 1 to 4 of Examples where the reoxidation temperature was higher than 900 ° C. and lower than 1150 ° C., the Mn element ratio (β / α) was within the scope of the present invention. All of these samples 1 to 4 had excellent IR lifetimes of 50 hours or more, and as shown in FIG. 5 and Table 1, the dielectric loss was low over a wide temperature range. In addition, when the temperature of the reoxidation treatment is set to a range higher than 900 ° C. and lower than 1150 ° C. by comparing the sample 1 and the sample 4, the Mn element ratio ( It can be confirmed that β / α) tends to be lower.

  On the other hand, in the samples 5 to 7 of the comparative examples in which the temperature of the reoxidation treatment was lower than the preferable range of the present invention and the sample 8 of the comparative example in which the reoxidation treatment was not performed, the Mn element ratio (β / Α) increased to 3.2 or more in all cases, and all resulted in inferior IR life. Furthermore, it can be confirmed from FIG. 5 that samples 6 to 8 have a high dielectric loss. Sample 5 had a good dielectric loss, but was inferior in terms of reliability because of its poor IR life.

  Further, in the sample 9 of the comparative example in which the reoxidation treatment was increased to 1200 ° C., the internal electrode was significantly interrupted or spheroidized and hardly functioned as a capacitor.

  From these results, by making the Mn element ratio (β / α) larger than 1 and 3.1 or less, the IR characteristics are excellent while maintaining the temperature characteristics of the dielectric constant and the capacitance, and − It was confirmed that the dielectric loss can be kept low in a wide temperature range of 55 to + 155 ° C. In addition, although not necessarily clear, in the samples 1-4 of a present Example, it is thought that some of the added Mn elements are unevenly distributed in the electrode interruption part. Further, from the results of Comparative Samples 5 to 8, when the temperature of the reoxidation treatment is low and when the reoxidation treatment is not performed, the Mn element ratio (β / α) tends to be out of the scope of the present invention. there were.

Example 2
In Example 2, a sample of the multilayer ceramic capacitor was obtained by the same method as Sample 1 in Example 1 except that the amount of addition of MnCO ₃ as the third subcomponent was changed as shown in Table 2. And the influence of the addition of Mn oxide was evaluated. In Example 2, the Mn element ratio (β / α), IR lifetime, and IR defect rate were evaluated in the same manner as in Example 1. The results are shown in Table 2. In Example 2, the reoxidation treatment was performed under the conditions of a treatment temperature of 1100 ° C., a wetter temperature of 35 ° C., and an oxygen partial pressure of 4.2 × 10 ⁻⁷ MPa.

  From Table 2, it can be confirmed that in samples 1, 10 to 14, the IR lifetime tends to deteriorate as the amount of Mn added increases. Among these, the samples 1 and 11 to 13 of the examples were excellent in IR life and all had good results.

  On the other hand, in the sample 10 of the comparative example in which Mn was not added, IR failure occurred, and the IR life could not be measured. Moreover, since Mn was not added to the sample 10 of the comparative example, the Mn element ratio (β / α) could not be measured. In addition, the sample 14 of the comparative example in which the addition amount of Mn was 5 mol had a Mn element ratio (β / α) as large as 3.5, resulting in inferior IR life.

FIG. 1 is a cross-sectional view of a multilayer ceramic capacitor according to an embodiment of the present invention. FIG. 2 is an enlarged cross-sectional view of a dielectric layer of the multilayer ceramic capacitor according to one embodiment of the present invention. FIG. 3 is a diagram for explaining a method for measuring the Mn element ratio (β / α) in the present invention. FIG. 4 is a graph showing the relationship of the Mn content in the grains and at the grain boundaries of the multilayer ceramic capacitor according to the example of the present invention. FIG. 5 is a graph showing the relationship between the measured temperature and the dielectric loss of the multilayer ceramic capacitor according to the example of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Multilayer ceramic capacitor 10 ... Capacitor element main body 2 ... Dielectric layer 21 ... Ceramic particle 22 ... Crystal grain boundary 3 ... Internal electrode layer 4 ... External electrode

Claims (3)

An electronic component having a dielectric layer,
The dielectric layer is made of a dielectric ceramic composition,
The dielectric ceramic composition is represented by a composition formula {(Ca _1−x Me _x ) O} _m · (Zr _1−y Ti _y ) O ₂ , and a symbol Me indicating an element name in the composition formula is: The symbols m, x, and y, which are at least one of Sr, Mg, and Ba and indicate the composition molar ratio, are 0.8 ≦ m ≦ 1.3, 0 ≦ x ≦ 1.00, and 0 ≦ y ≦ 0.8. A main component containing a dielectric oxide in the relationship of
A first subcomponent comprising an oxide of V;
A second subcomponent comprising an oxide of Al;
A third subcomponent containing an oxide of Mn,
The ratio of each component to 100 moles of the main component is
First subcomponent: 0 mole <first subcomponent <7 moles (note _that the value in terms of V 2 _{O 5),}
Second subcomponent: 0 mol <second subcomponent <15 mol (however, converted to Al ₂ O ₃ ),
Third subcomponent: 0 mol <third subcomponent <5 mol (however, in terms of Mn element in the oxide of Mn) ,
The dielectric ceramic composition has a plurality of ceramic particles and a grain boundary existing between the adjacent ceramic particles,
Content ratio (α) of Mn element in the ceramic particles with respect to all elements constituting the dielectric layer, and content ratio (β) of Mn element in the crystal grain boundary with respect to all elements constituting the dielectric layer And an Mn element ratio (β / α) that is greater than 1 and less than or equal to 3.1. The dielectric ceramic composition is
The SiO ₂ as a main component, MO (provided that, M is at least one element selected from Ba, Ca, Sr and Mg), fourth sub comprises at least one selected from Li ₂ O and _B 2 _{O 3} Further containing ingredients,
2. The electronic component according to claim 1 , wherein a ratio of the fourth subcomponent to 100 mol of the main component is 0 mol <fourth subcomponent <20 mol in terms of oxide. The fourth subcomponent is represented by a composition formula {(Ba _z , Ca _1−z ) O} _v SiO ₂ , and symbols z and v indicating a composition molar ratio in the composition formula are 0 ≦ z ≦ 1 and The electronic component according to claim 2 , comprising a composite oxide having a relationship of 0.5 ≦ v ≦ 4.0.