JP4899342B2 - Ceramic electronic component and manufacturing method thereof - Google Patents

Ceramic electronic component and manufacturing method thereof Download PDF

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JP4899342B2
JP4899342B2 JP2005149932A JP2005149932A JP4899342B2 JP 4899342 B2 JP4899342 B2 JP 4899342B2 JP 2005149932 A JP2005149932 A JP 2005149932A JP 2005149932 A JP2005149932 A JP 2005149932A JP 4899342 B2 JP4899342 B2 JP 4899342B2
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陽 佐藤
真理 宮内
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Tdk株式会社
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  The present invention relates to a ceramic electronic component such as a multilayer ceramic capacitor and a manufacturing method thereof. More specifically, even when a dielectric layer constituting a ceramic electronic component is thinned, an IR defect rate can be kept low. The present invention relates to a possible ceramic electronic component and a manufacturing method thereof.

  A multilayer ceramic capacitor, which is an example of an electronic component, can be obtained by, for example, simultaneously firing a green chip obtained by alternately stacking ceramic green sheets made of a predetermined dielectric material and internal electrode layers of a predetermined pattern, and then integrating them. Manufactured. Since the internal electrode layer of the multilayer ceramic capacitor is integrated with the ceramic dielectric by firing, it is necessary to select a material that can withstand firing in an oxidizing atmosphere. For this reason, as a material constituting the internal electrode layer, conventionally, an expensive noble metal such as platinum or palladium has been inevitably used.

  On the other hand, in order to use an inexpensive base metal (for example, nickel or copper) as a material for the internal electrode, it does not become a semiconductor even if it is fired at a low temperature in a neutral or reducing atmosphere, that is, it has reduced resistance. It is necessary to develop a dielectric ceramic composition that is excellent and has a sufficient dielectric constant and excellent dielectric properties (for example, a small rate of change in capacitance temperature) after firing.

  Conventionally, various proposals have been made as dielectric ceramic compositions in which a base metal can be used as a material for internal electrodes.

For example, Patent Documents 1 to 3 disclose dielectric ceramic compositions mainly composed of a dielectric oxide having a composition represented by (Sr 1-x Ca x ) m (Ti 1-y Zr y ) O 3. Has been. However, the dielectric ceramic compositions described in these documents are prone to deterioration in insulation resistance (IR). Therefore, when the dielectric ceramic composition is used for the dielectric layer and the base metal element is used for the internal electrode layer. There is a problem that the defective rate of the initial insulation resistance of the obtained multilayer ceramic capacitor is increased, and particularly when the dielectric layer is made thinner, the increase of the defective rate is remarkable.

On the other hand, in order to improve the defect rate of the initial insulation resistance, the present applicant has previously described {(Sr 1-x Ca x ) O} m · (Ti 1 -Y Zr y ) In a dielectric ceramic composition whose main component is a dielectric oxide having the composition represented by O 2 , the values of x, y and m of this dielectric oxide are within a predetermined range, and various subcomponents A dielectric porcelain composition to which is added is proposed. By using the dielectric ceramic composition described in these documents, good results are obtained even when the thickness of the dielectric layer constituting the multilayer ceramic capacitor is reduced to about 4 μm.

  On the other hand, in recent years, there is a high demand for downsizing of electronic components due to higher density of electronic circuits, and downsizing and increasing capacity of multilayer ceramic capacitors are rapidly progressing. In order to cope with this reduction in size and increase in capacity, the thickness of the dielectric layer constituting the multilayer ceramic capacitor is steadily decreasing.

  However, in the above-mentioned Patent Documents 4 to 7, when the dielectric layer is further thinned, specifically, when the thickness of the dielectric layer is about 2 μm or less, the defect rate of the initial insulation resistance is kept low. Is getting harder. Therefore, it has been difficult for the dielectric compositions described in these documents to cope with further thinning of the dielectric layer.

In addition to the above, the applicant of the present invention has disclosed in Patent Document 8 a main component represented by the composition formula (AO) m · BO 2 (in the composition formula, the element A is at least selected from Sr, Ca, and Ba). In the method of manufacturing a dielectric ceramic composition having one element, element B being at least one element of Ti and Zr), the molar ratio in the composition formula is represented by the composition formula (AO) m ′ · BO 2. A method of manufacturing a dielectric ceramic composition using a raw material where m ′ is m ′ <m is proposed. In this document, in the example, when m = 0.985, the value of the raw material m ′ is made smaller than the value of the final m as the thickness of the dielectric layer is reduced to 4 μm and 2 μm. Is described as effective. However, in this document, particularly when the thickness of the dielectric layer is set to 2 μm, the IR defect rate exceeds 60%. Therefore, even if the IR defect rate can be reduced as in this document, the IR defect rate is further deteriorated when the number of dielectric layers is increased and the number of dielectric layers is increased. End up. Therefore, it has been difficult to cope with further thinning of the dielectric layer even by the method described in this document.

JP 63-224108 A JP 63-224109 A JP-A-4-206109 JP 2001-220229 A Japanese Patent Laid-Open No. 2002-294938 Japanese Patent Laid-Open No. 2002-80278 JP 2002-80279 A JP 2001-342060 A

  The present invention has been made in view of such a situation, and can be fired in a reducing atmosphere in a ceramic electronic component such as a multilayer ceramic capacitor, and has a capacitance-temperature characteristic of X6S characteristic (−55 to 105 ° C. of EIA standard). , ΔC / C = within ± 22%), and the IR defect rate is kept low even when the dielectric layer constituting the ceramic electronic component is thinned (for example, about 2 μm). It is an object of the present invention to provide a ceramic electronic component that can be used, and a method for manufacturing the same.

In order to achieve the above object, a ceramic electronic component according to the present invention comprises:
A ceramic electronic component containing a dielectric layer,
The dielectric layer includes a main component including a dielectric oxide having a composition represented by {(Sr 1-x Ca x ) O} m · (Ti 1-y Zr y ) O 2 ;
A first subcomponent including MgO and / or Al 2 O 3, containing,
The symbols m, x and y indicating the composition molar ratio in the formula contained in the main component are
1.005 ≦ m <1.1,
0 ≦ x ≦ 1.0,
0 ≦ y ≦ 0.4,
The ratio of the first subcomponent to 100 mol of the main component is 0.05 to 3 mol in terms of MgO or Al 2 O 3 .

  In the ceramic electronic component of the present invention, the thickness of the dielectric layer is preferably 2 μm or less, more preferably 1.8 μm or less.

  In the ceramic electronic component of the present invention, the average crystal grain size of the dielectric particles constituting the dielectric layer is preferably 2 μm or less, more preferably 1 μm or less, and even more preferably 0.5 μm or less.

In the ceramic electronic component of the present invention, preferably, the dielectric layer further contains a glass component, and the content of the glass component is 0.01 to 15 mol with respect to 100 mol of the main component. is there. In the present invention, the glass component preferably contains silicon oxide. For example, SiO 2 which is an oxide of Si alone, SiO 2 and Ba oxide or Ca oxide are mixed. And Si-containing composite oxides obtained by heat treatment.

  In the ceramic electronic component of the present invention, preferably, the dielectric layer further includes a second subcomponent including an oxide of Mn, and a ratio of the second subcomponent to 100 mol of the main component is MnO. In terms of conversion, it is 0 to 4 (excluding 0) moles.

In the ceramic electronic component of the present invention, preferably, the dielectric layer includes an oxide of R (where R is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy). , Ho, Er, Tm, Yb and Lu) and / or a fourth subcomponent containing an oxide of V, Nb, W, Ta, and Mo, Contains
In the case of containing the third subcomponent, the ratio of the third subcomponent to 100 mol of the main component is 6 mol or less in terms of R element,
In the case of containing the fourth subcomponent, the ratio of the fourth subcomponent to 100 mol of the main component is 2 mol or less in terms of a metal element in the oxide.

  In the present invention, in addition to the main component, the first subcomponent, and the glass component and the second subcomponent that are preferably added to the dielectric layer, if necessary, the predetermined amount of the third subcomponent is included in the dielectric layer. And / or the 4th subcomponent may be contained.

A method for producing a ceramic electronic component according to the present invention is a method for producing any one of the above ceramic electronic components,
Preparing a dielectric material that will constitute the dielectric layer after firing;
Firing the dielectric material, and
When preparing the dielectric material, as the material of the first subcomponent, an oxide of A (wherein symbol A is one or more elements selected from Mg and Al) and / or A after firing The compound to be an oxide is used without previously reacting with other components that constitute the dielectric material,
Firing is performed in the form of an oxide of A alone and / or in the form of a compound alone which becomes an oxide of A after firing.

  The ceramic electronic component of the present invention and the ceramic electronic component obtained by the manufacturing method of the present invention are not particularly limited, but include multilayer ceramic capacitors, piezoelectric elements, chip inductors, chip varistors, chip thermistors, chip resistors, and other surface mounts. (SMD) chip type electronic components are exemplified.

According to the present invention, in a ceramic electronic component such as a multilayer ceramic capacitor, the dielectric layer contained in these electronic components includes the predetermined main component and a first subcomponent including MgO and / or Al 2 O 3. Have. Therefore, the capacitance-temperature characteristic satisfies the EIA standard X6S characteristic (−55 to 105 ° C., ΔC / C = ± 22% or less), and even when the dielectric layer constituting the ceramic electronic component is thinned, It is possible to keep the IR defect rate low. In particular, according to the present invention, even when the dielectric layer is thinned to 2 μm or less, preferably 1.8 μm or less, the IR defect rate can be kept low, so that the ceramic electronic component can be reduced in size and capacity. It becomes possible.

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.

Multilayer ceramic capacitor 1
As shown in FIG. 1, a multilayer ceramic capacitor 1 according to an embodiment of the present invention includes a capacitor element body 10 having a configuration 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 shape of the capacitor element body 10 is not particularly limited, but is usually a rectangular parallelepiped shape. 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.

  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.

Dielectric layer 2
The dielectric layer 2 contains a dielectric ceramic composition.
In the present embodiment, the dielectric ceramic composition includes a main component including a dielectric oxide having a composition represented by {(Sr 1-x Ca x ) O} m · (Ti 1-y Zr y ) O 2. And a first subcomponent containing MgO and / or Al 2 O 3 . At this time, the amount of oxygen (O) may be slightly deviated from the stoichiometric composition of the above formula.

  In the above formula, x is 0 ≦ x ≦ 1.0, preferably 0.1 ≦ x ≦ 0.5. x represents the number of Ca atoms, and the phase transition point of the crystal can be arbitrarily shifted by changing x, that is, the Ca / Sr ratio. Therefore, the capacity temperature coefficient and the relative dielectric constant can be arbitrarily controlled. By setting x in the above range, the phase transition point of the crystal exists near room temperature, and the capacity-temperature characteristics can be improved. If x is too large, the dielectric constant tends to be low. On the other hand, if x is too small, the capacity-temperature characteristic tends to deteriorate. However, in the present invention, the ratio of Ca and Sr is arbitrary, and only one of them may be contained.

In the above formula, y is 0 ≦ y ≦ 0.4, preferably 0 ≦ y ≦ 0.2. Although y represents the number of Zr atoms, there is a tendency that the reduction resistance is further increased by substituting ZrO 2 which is difficult to reduce compared to TiO 2 . However, in the present invention, Zr may not necessarily be included, and only Ti may be included.

  In the above formula, m is 1.005 ≦ m <1.1, preferably 1.005 ≦ m ≦ 1.05. By setting m to 1.005 or more, the grain growth of the dielectric particles during firing can be suppressed, and the dielectric particles constituting the dielectric layer after firing can be miniaturized. Further, by setting m to less than 1.1, a dense sintered body can be obtained without increasing the firing temperature. If m is too small, it is difficult to make the dielectric particles fine and the IR defect rate tends to deteriorate. On the other hand, if m is too large, the sintering temperature becomes too high and sintering tends to be difficult.

Content of the first subcomponent including MgO and / or Al 2 O 3, relative to the main component as 100 mol, of MgO or Al 2 O 3 in terms of a 0.05 to 3 mol, preferably 0. 07-3 moles. When the main component composition is in the above range and MgO and / or Al 2 O 3 is contained in the predetermined range, the IR defect rate can be kept low even when the dielectric layer is thinned. In the present invention, it is sufficient to contain at least one of said MgO and Al 2 O 3 but, MgO, may contain both Al 2 O 3. However, MgO, when containing both of Al 2 O 3, the total content of MgO and Al 2 O 3 is within the above range.

If the content of the first subcomponent containing MgO and / or Al 2 O 3 is too small, the IR defect rate is deteriorated and it is difficult to reduce the thickness of the dielectric layer. On the other hand, when the content is too large, the capacity-temperature characteristic is deteriorated and the X6S characteristic may not be satisfied.

Conventionally, when the dielectric layer is thinned, the cause of the deterioration of the IR defect rate is, for example, as follows.
That is, conventionally, a base material {(Sr 1-x Ca x ) O} m · (Ti 1-y Zr y) TiO 2 released from O 2 is reduced to TiO 2n-1 during the reduction firing As a result, oxygen deficiency occurred. The TiO 2n-1 in which oxygen vacancies are generated remains in the particle interface and particles in the fired dielectric layer, causing a decrease in the particle interface and particle resistance. As a result, the dielectric It is considered that the resistance of the layer was lowered and the IR defect rate was deteriorated. This tendency is due to the influence of the particle interface and particles having such reduced resistance as the thickness of the dielectric layer is reduced and the number of dielectric particles per layer of the dielectric layer is reduced. There was a tendency for the deterioration of the IR defect rate to become remarkable. Therefore, conventionally, it is considered that when the dielectric layer is thinned, the IR defect rate is deteriorated.

In contrast, in the present invention, since a predetermined amount of MgO and / or Al 2 O 3 is contained in the dielectric layer, the IR defect rate is deteriorated even when the dielectric layer is thinned. Can be effectively prevented. Although this reason is not necessarily clear, the following reasons are conceivable.
That is, MgO reacts with TiO 2n-1 generated during reduction firing to become MgTiO 3 which is a composite oxide, which is considered to have an effect of preventing the occurrence of oxygen deficiency.
In addition, Al 2 O 3 has an effect of suppressing the grain growth of dielectric particles during firing, so that the number of dielectric particles per layer can be increased, and as a result, the IR defect rate can be kept low. It is thought that you can. Al 2 O 3 is considered to have an effect of suppressing generation of TiO 2n-1 at the dielectric particle interface.

  It is preferable that the dielectric ceramic composition constituting the dielectric layer 2 further contains a glass component and a second subcomponent containing an oxide of Mn.

Although it does not specifically limit as a glass component, It is preferable that it contains a silicon oxide. Examples of such glass components, for example, other SiO 2 an oxide of Si alone, by mixing the oxides of oxides and Ca of SiO 2 and Ba, Si-containing complex oxide obtained by heat treating Etc. As such a Si-containing composite oxide, a compound represented by (Ba, Ca) x SiO 2 + x (where x = 0.7 to 1.2) can be used. In addition, the ratio of Ba and Ca is arbitrary and may contain only one side.

  The glass component content is preferably 0.01 to 15 mol, more preferably 0.1 to 3 mol, with respect to 100 mol of the main component. When the content of the glass component is too small, the IR defect rate may be deteriorated. On the other hand, if the amount is too large, the relative permittivity tends to decrease.

  The second subcomponent (Mn oxide) has the effect of promoting sintering and the effect of improving the high temperature load life. The content of the second subcomponent is preferably 0 to 4 mol (excluding 0), more preferably 0.1 to 1 mol, in terms of MnO, with respect to 100 mol of the main component. If the content of the second subcomponent is too small, the effect of improving the high temperature load life tends to be insufficient. On the other hand, if the content is too large, the IR defect rate may deteriorate.

  In the present embodiment, the dielectric ceramic composition constituting the dielectric layer 2 includes the main component, the first subcomponent, and the glass component and the second subcomponent that are preferably added, as necessary. , R oxide (wherein R is at least one selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) A third subcomponent including seeds and / or a fourth subcomponent including oxides of V, Nb, W, Ta, and Mo may further be included.

  The third subcomponent (R oxide) has the effect of improving the high temperature load life. When the third subcomponent is contained, the ratio of the third subcomponent to 100 mol of the main component is preferably 6 mol or less, more preferably 2 mol or less, still more preferably 0.01 to 1 in terms of R element. Is a mole. If the content of the third subcomponent is too small, the above effect cannot be obtained. On the other hand, if too much, the firing temperature tends to be too high. Among R elements, Y, Dy, Ho, and Yb are preferable, and Y is particularly preferable.

  The fourth subcomponent (oxide of V, Nb, W, Ta, Mo) has an effect of improving the high temperature load life. When the fourth subcomponent is contained, the ratio of the fourth subcomponent to 100 mol of the main component is preferably 2 mol or less, more preferably 0.005 to 0.1 mol in terms of the metal element in the oxide. It is. If the content of the fourth subcomponent is too small, the above effect cannot be obtained. On the other hand, if too much, IR tends to decrease. Among the fourth subcomponents, the oxide of V is preferable because the effect of improving the high temperature load life is particularly high.

The average crystal grain size of the dielectric particles constituting the dielectric layer 2 is preferably miniaturized to 2 μm or less, more preferably 1 μm or less, and further preferably 0.5 μm or less. Since the dielectric layer 2 of the present embodiment has the composition of the main component within the above predetermined range and contains the first subcomponent MgO and / or Al 2 O 3 , the dielectric layer 2 is made finer. Is possible. The average crystal grain size of the dielectric particles can be measured, for example, from a SEM image of the dielectric particles by a code method in which the average particle size is measured assuming that the shape of the dielectric particles is a sphere.

  The thickness of the dielectric layer 2 is preferably 2 μm or less, and more preferably 1.8 μm or less. In this embodiment, since the dielectric ceramic composition contained in the dielectric layer 2 has the above configuration, even when the dielectric layer 2 is thinned to 2 μm or less, and further to 1.8 μm or less, It is possible to effectively prevent the deterioration of the IR defect rate.

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 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 internal electrode layer 3 may be formed using a commercially available electrode paste. What is necessary is just to determine the thickness of the internal electrode layer 3 suitably according to a use etc.

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. What is necessary is just to determine the thickness of the external electrode 4 suitably according to a use etc.

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 material (dielectric ceramic composition powder) contained in the dielectric layer paste is prepared, and this 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.

  As the dielectric material, the above-mentioned main component and subcomponent oxides, mixtures thereof, and complex oxides can be used. In addition, various compounds that become the above-described oxides and complex oxides by firing, such as carbonic acid, can be used. A salt, an oxalate salt, a nitrate salt, a hydroxide, an organometallic compound, or the like can be selected as appropriate and used in combination. What is necessary is just to determine content of each compound in a dielectric raw material so that it may become a composition of the above-mentioned dielectric ceramic composition after baking. In the state before forming a paint, the particle size of the dielectric material is usually about 0.1 to 1 μm in average particle size.

In the present embodiment, as a raw material for the first subcomponent (MgO or Al 2 O 3 ), an oxide of A (where symbol A is one or more elements selected from Mg and Al) and / or A compound which becomes an oxide of A after firing and a form of the oxide of A alone and / or a compound which becomes an oxide of A after firing, without previously reacting the compound which becomes an oxide of A after firing with other components constituting the dielectric material. It is preferably used in a single form. That is, as the first subcomponent raw material, an oxide of Mg, an oxide of Al, a compound that becomes an oxide of Mg after firing, and a compound that becomes an oxide of Al after firing are used in a single form. preferable.

The oxide of A as the raw material of the first subcomponent and the compound that becomes the oxide of A after firing are added to the dielectric raw material in a single form, and each is in a single form without being calcined in advance. By firing, the effect of adding the first subcomponent (MgO or Al 2 O 3 ) can be sufficiently exerted. On the other hand, for example, the raw materials for these first subcomponents are preliminarily calcined together with other subcomponents and glass components, not in the form of an oxide of A alone, a compound that becomes an oxide of A after firing, When roasted powder is used, the above-mentioned effects tend not to be obtained.

When the symbol A is Mg, the Mg oxide is exemplified by MgO, and the compounds that become Mg oxide after firing are MgCO 3 , Mg (OH) 2, and water thereof. Examples of the hydrates include hydrates mainly composed of Mg. Further, when the symbol A is Al, Al 2 O 3 is exemplified as the Al oxide, and Al (OH) 3 or its hydration is used as the compound that becomes the Al oxide after firing. And other hydrates mainly composed of Al. A plurality of these oxides and compounds may be used. That is, for example, as a raw material that becomes MgO after firing, an MgO powder that is an oxide and an MgCO 3 powder that is a carbonate may be mixed at an arbitrary ratio.

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

  The internal electrode layer paste and the external electrode paste may be commercially available electrode pastes, or may be pastes of commercially available electrode materials.

  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 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. 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 firing atmosphere is air or a reducing atmosphere.

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 −10 to 10 −3 Pa. 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 1000-1400 degreeC, More preferably, it is 1100-1360 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, the electrode is interrupted due to abnormal sintering of the internal electrode layer, the capacity-temperature characteristic is deteriorated due to diffusion of the internal electrode layer constituent material, Reduction of the body porcelain composition 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 can be used by humidification.

  When firing in a reducing atmosphere, it is preferable to anneal the capacitor element body. Annealing is a process for re-oxidizing the dielectric layer, and this can significantly increase the IR lifetime, thereby improving the reliability.

The oxygen partial pressure in the annealing atmosphere is preferably 10 −1 to 10 Pa. When the oxygen partial pressure is less than the above range, it is difficult to reoxidize the dielectric layer, and when it exceeds the above range, the internal electrode layer tends to be oxidized.

  The holding temperature at the time of annealing is preferably 1100 ° C. or less, particularly 500 to 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 high temperature load life is likely to be shortened. On the other hand, when 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, and the high temperature is increased. The load 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 10 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 the present invention thus manufactured is mounted on a printed circuit board by soldering or the like and used for various electronic devices.

  As mentioned above, although embodiment of this invention was 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 ceramic electronic component according to the present invention. However, the ceramic electronic component according to the present invention is not limited to the multilayer ceramic capacitor, and has a dielectric layer having the above configuration. 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, a dielectric material for preparing a dielectric ceramic composition constituting the dielectric layer was prepared.
In this example, in order to manufacture sample numbers 1 to 15 shown in Table 1, dielectric materials corresponding to each sample were prepared.

Sample numbers 1-5
That is, in sample numbers 1 to 5, {(Sr 1−x Ca x ) O} m · (Ti 1−y Zr y ) O 2 obtained by the sol-gel method as the main component material, and the subcomponent material , MnO, Y 2 O 3 , V 2 O 5 and MgO and glass components (BaO—CaO—SiO 2 and CaO—SiO 2 ) were prepared, wet-mixed by a ball mill for 16 hours, and dried. A dielectric material was used. The x, y, m in the main component, the addition amount of each subcomponent, and the type and addition amount of the glass component were as shown in Table 1. Further, as BaO-CaO-SiO 2 is a glass component, a (Ba 0.42 Ca 0.58) SiO 3 , as the CaO-SiO 2, the CaO · SiO 2, were used, respectively. These glass components were prepared by mixing an oxide or carbonate as a raw material with water, firing in air at a temperature of 1000 ° C. for 3 hours, and then pulverizing.

Sample numbers 6-10
Similarly, in sample numbers 6 to 10, dielectric materials were prepared using Al 2 O 3 instead of MgO as the first subcomponent material. However, in sample number 11, Y 2 O 3 was not used.

Sample numbers 11 and 12
Similarly, in Sample Nos. 11 and 12, dielectric materials were prepared using MgO and Al 2 O 3 as the first subcomponent material. However, in sample number 14, Y 2 O 3 was not used.

Sample numbers 13-15
Similarly, in Sample Nos. 13 to 15, a dielectric material was prepared without using any of MgO and Al 2 O 3 . In Sample No. 13, (Ba 0.42 Ca 0.58 ) SiO 3 is used as a glass component, in Sample No. 14, CaO.SiO 2 is used as a glass component, and in Sample No. 15, SiO is used as a glass component. 2 were used respectively.

  Next, 100 parts by weight of the obtained dielectric material, 10 parts by weight of polyvinyl butyral resin, 5 parts by weight of dibutyl phthalate (DOP) as a plasticizer, and 100 parts by weight of alcohol as a solvent are mixed with a ball mill to obtain a paste. To obtain a dielectric layer paste.

  In this example, a capacitor electrode paste (a paste mainly containing Ni particles as conductive particles) was used as the internal electrode layer paste.

  Using these pastes, the multilayer ceramic chip capacitor 1 shown in FIG. 1 was manufactured as follows.

  First, a green sheet was formed on a PET film by the doctor blade method using the obtained dielectric layer paste. Next, an electrode pattern was printed on the green sheet by screen printing using the internal electrode layer paste to produce a green sheet on which the electrode pattern was printed. Next, separately from the above green sheet, a green sheet with no electrode pattern printed on the PET film was manufactured by a doctor blade method using the dielectric layer paste.

And each green sheet manufactured above was laminated | stacked in the following order, and the green chip | tip was manufactured by pressing the obtained laminated body.
First, green sheets on which no electrode patterns were printed were laminated until the total thickness reached 300 μm. On top of that, five green sheets printed with electrode patterns were laminated. Further thereon, a green sheet on which no electrode pattern was printed was laminated until the total thickness reached 300 μm to obtain a laminate. The obtained laminate was heated and pressurized under the conditions of a temperature of 80 ° C. and a pressure of 1 t / cm 2 to obtain a green chip.

Next, the obtained green chip was cut into a predetermined size and subjected to binder removal processing, firing and annealing under the following conditions to obtain a multilayer ceramic fired body.
The binder removal treatment conditions were temperature rising rate: 30 ° C./hour, holding temperature: 250 ° C., temperature holding time: 8 hours, and atmosphere: in the air.
The firing conditions were as follows: temperature rising rate: 300 ° C./hour, holding temperature: each temperature shown in Table 1, temperature holding time: 2 hours, cooling rate: 300 ° C./hour, atmospheric gas: humidified N 2 and H 2 A mixed gas (oxygen partial pressure: 6 × 10 −10 to 5 × 10 −4 Pa) was used.
The annealing conditions were: temperature rising rate: 300 ° C./hour, holding temperature: 1000 ° C., temperature holding time: 2 hours, cooling rate: 300 ° C./hour, atmospheric gas: humidified N 2 gas (oxygen partial pressure: 10 −1 Pa).
Note that a wetter with a water temperature of 20 ° C. 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 sand blasting, In-Ga was applied as an external electrode to obtain samples 1 to 15 of the multilayer ceramic capacitor shown in FIG. The size of the obtained capacitor sample is 3.2 mm × 1.6 mm × 1.0 mm, the thickness of the dielectric layer is 2 μm, the thickness of the internal electrode layer is 1.5 μm, and the dielectric layer sandwiched between the internal electrode layers is The number was 4.

  For each of the obtained capacitor samples, the average crystal grain size, IR defect rate, capacitance temperature characteristic, and relative dielectric constant of the dielectric particles constituting the dielectric layer were measured by the following methods.

Average crystal grain size of dielectric particles First, the obtained capacitor sample was cut along a plane perpendicular to the internal electrode, the cut surface was polished, and then this polished surface was subjected to chemical etching. Thereafter, observation was performed with a scanning electron microscope (SEM), and the average crystal grain size of the dielectric particles was measured by a code method assuming that the shape of the dielectric particles was a sphere. The average crystal grain size was an average value of 250 measurement points. The results are shown in Table 1.

IR failure rate First, using an insulation resistance meter (R8340A manufactured by Advantest), DC12.5V was applied to the capacitor samples for 60 seconds under the conditions of room temperature, and the insulation resistance after voltage application IR was measured on 200 samples. Next, the maximum value of the insulation resistance value of 200 samples was calculated, and the sample in which the insulation resistance value was one digit lower than the maximum value (the insulation resistance was 1/10 or less of the maximum value). Sample) was defined as a defective product, and the occurrence rate of defective products was defined as an IR defect rate. The smaller this value, the lower the IR defect rate and the more non-defective products. In this example, 5% or less is preferable. The results are shown in Table 1.

Capacitance-temperature characteristics For the capacitor sample, the capacitance at each temperature of −55 ° C., 25 ° C., and 105 ° C. was measured, and the change rate ΔC of the capacitance at −55 ° C. and 105 ° C. with respect to the capacitance at 25 ° C. (Unit:%) was calculated. In this example, a sample in which the rate of change in electrostatic capacitance satisfies the X6S characteristic of the EIA standard (−55 to 105 ° C., ΔC = within ± 22%) is considered good. The results are shown in Table 1. In Table 1, samples that satisfy the X6S characteristics are indicated by “◯”, and samples that do not satisfy the X6S characteristics are indicated by “X”.

Dielectric constant (ε r )
First, at a reference temperature of 25 ° C., a capacitor with a frequency of 1 kHz and an input signal level (measurement voltage) of 1.0 Vrms is input with a digital LCR meter (YHP 4284A), and the capacitance C is measured. did. The relative dielectric constant ε r (no unit) was calculated based on the thickness of the dielectric layer, the effective electrode area, and the capacitance C obtained as a result of the measurement. As a result of the measurement, all of the samples of this example had a relative dielectric constant ε r of 150 or more, which was a favorable result.

Table 1 shows the main component composition of sample numbers 1 to 15, the added amount of each subcomponent, the type and added amount of the added glass component, the firing temperature, the average crystal grain size of the dielectric particles, the IR defect rate, and the capacity-temperature characteristics. (X6S) and evaluation as a capacitor are shown. In this example, a sample having an IR defect rate of 5% or less and a capacity-temperature characteristic satisfying X6S was evaluated as good (“◯” in the table), and a sample that did not satisfy any of the samples was evaluated. And evaluated as bad ("X" in the table) (the same applies to Tables 2 to 4). In Table 1, the content of auxiliary component and the glass component, the number of moles relative to 100 moles of the main component (however, Y 2 O 3, V 2 O 5 , respectively, Y terms of element number of moles of V in terms of element) (Table 2 to Table 4 are also the same).

By comparing sample numbers 1 to 5, x, y, and m of {(Sr 1-x Ca x ) O} m · (Ti 1-y Zr y ) O 2 as the main component are determined within the predetermined range of the present invention. In the case where MgO, which is the first subcomponent, is contained in the range of 0.05 to 3 mol (sample numbers 2 to 4), the IR defect rate is 5% or less and further satisfies the X6S characteristic. As a result. On the other hand, in sample number 1 where the content of MgO as the first subcomponent was 0.01 mol, the IR defect rate deteriorated, and in sample number 5 where the content of MgO was 4 mol As a result, the capacity-temperature characteristic deteriorated and the X6S characteristic was not satisfied.

Similarly, by comparing sample numbers 6 to 10, it was confirmed that even when Al 2 O 3 was used as the first subcomponent, the same result as that obtained when MgO was used was obtained.

Further, from Sample Nos. 11 and 12, even when two kinds of MgO and Al 2 O 3 are added as the first subcomponent, the total amount of the first subcomponent is in the range of 0.05 to 3 mol. It was confirmed that the IR defect rate could be reduced to 5% or less and that the capacity-temperature characteristic satisfied the X6S characteristic.

In contrast, in sample numbers 13 to 15 in which neither MgO nor Al 2 O 3 as the first subcomponent was contained, the IR defect rate exceeded 5%, and the IR defect rate was reduced. The result was inferior.

Example 2
The main component {(Sr 1-x Ca x ) O} m · (Ti 1-y Zr y ) O 2 represents x, y, m, the added amount of each subcomponent, the type and added amount of the glass component. Capacitor samples 16 to 18 were produced in the same manner as in Example 1 except that the changes were made as shown in FIG. And about the obtained capacitor | condenser sample, the average crystal grain diameter of dielectric particle | grains, IR defect rate, a capacitance temperature characteristic, and a dielectric constant were measured like Example 1. FIG. The results are shown in Table 2.

In Table 2, sample number 16 is a sample in which V 4 O 5 as the fourth subcomponent was not used, and sample numbers 17 and 18 are samples in which the value of x of the main component was changed. .

From Table 2, the IR defect rate is reduced to 5% or less even when V 2 O 5 is not contained and when the x value of the main component is x = 0.2 and 0.4, respectively. In addition, it was confirmed that the capacity-temperature characteristic satisfies the X6S characteristic. Sample Nos. 16 to 18 in Table 2 all had a relative dielectric constant ε r of 150 or more, which was a good result.

Example 3
The main component {(Sr 1-x Ca x ) O} m · (Ti 1-y Zr y ) O 2 represents x, y, m, the added amount of each subcomponent, the type and added amount of the glass component. Capacitor samples 19 to 22 were produced in the same manner as in Example 1 except that the change was made as shown in FIG. And about the obtained capacitor | condenser sample, the average crystal grain diameter of dielectric particle | grains, IR defect rate, a capacitance temperature characteristic, and a dielectric constant were measured like Example 1. FIG. The results are shown in Table 3.

In Table 3, sample numbers 19 to 21 are samples in which the value of m of the main component is outside the scope of the present invention. Sample No. 22 is a sample in which Al 2 O 3 is added as a glass component. Specifically, Al 2 O 3 is not a single oxide but is calcined together with CaO and SiO 2 in advance. was used which was 2 O 3 · CaO · SiO 2 .

Al 2 O 3 · CaO · SiO 2 as the glass component was prepared by the following method. That is, first, the oxide or carbonate as a raw material was weighed so that the molar ratio was Al 2 O 3 : CaO: SiO 2 = 1: 1: 1. Then, the weighed raw materials were mixed with water, fired in air at a temperature of 1000 ° C. for 3 hours, and then pulverized. The molecular weight of each of the components constituting the Al 2 O 3 · CaO · SiO 2 is, Al 2 O 3: 100.1702g / mol, CaO: 56.0794g / mol, SiO 2: is 60.0848g / mol . In the present embodiment, the molecular weight of Al 2 O 3 · CaO · SiO 2 is a glass component, as 216.3344g / mol of the sum of the molecular weight of each component was calculated number of moles. Specifically, Al 2 O 3 .CaO.SiO 2 1 mol was calculated as 216.3344 g.

From Table 3, the sample numbers 19 and 20 in which the value of m of the main component is m = 0.999 which is outside the scope of the present invention, the content of MgO or Al 2 O 3 is within the scope of the present invention. Nevertheless, the IR defect rate deteriorated. Further, in the sample number 21 in which the value of m of the main component is m = 1.1, which is outside the range of the present invention, and in the sample number 22 in which Al 2 O 3 is added as a glass component, the sinterability deteriorates. Therefore, even if the sintering temperature was sufficiently high as 1380 ° C., it could not be sintered.

Example 4
The auxiliary components MnO, Y 2 O 3 , V 2 O 5 and the glass component CaO · SiO 2 are calcined in advance at a temperature of 700 ° C. for 2 hours, and then pulverized and roasted. A capacitor sample No. 23 shown in Table 4 was produced in the same manner as in Example 1 except that the powder was used.
Similarly, except that the auxiliary components MnO, Y 2 O 3 , V 2 O 5 and MgO are preliminarily calcined under conditions of a temperature of 700 ° C. for 2 hours, and then pulverized to obtain a roasted powder. In the same manner as in Example 1, a capacitor sample No. 24 shown in Table 4 was produced.

In addition, in sample numbers 23 and 24, x, y, m of the main component {(Sr 1−x Ca x ) O} m · (Ti 1−y Zr y ) O 2 , and the addition amount of each subcomponent The types and addition amounts of the glass components were as shown in Table 4.

  From Table 4, sub-components and glass components other than MgO as the first sub-component are preliminarily calcined, and in sample number 23 added as roasted powder, the IR defect rate can be reduced to 5% or less, In addition, it was confirmed that the capacity-temperature characteristic satisfies the X6S characteristic. On the other hand, in the sample number 24 in which MgO as the first subcomponent and other subcomponents were calcined in advance and added as roasted powder, the IR defect rate was deteriorated.

Evaluation From the results of Examples 1 to 4 described above, the values of x, y, and m of {(Sr 1−x Ca x ) O} m · (Ti 1−y Zr y ) O 2 as the main component are within a predetermined range. In addition, the content of the first subcomponent MgO and Al 2 O 3 is 0.05 to 3 mol, so that the capacitance-temperature characteristic satisfies the X6S characteristic and the thickness of the dielectric layer is reduced. It was confirmed that the IR defect rate could be reduced even when the layer thickness was reduced to 2 μm. In particular, from the results of sample number 22 in Example 3 and the results of sample numbers 23 and 24 in Example 4, it is preferable that these first subcomponents be added as MgO alone or Al 2 O 3 alone. Can be confirmed.

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

Explanation of symbols

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

Claims (6)

  1. A ceramic electronic component containing a dielectric layer,
    It said dielectric layer includes a main component a dielectric oxide of a composition represented by {(Sr 1-x Ca x ) O} m · (Ti 1-y Zr y) O 2,
    A first auxiliary component composed of MgO and / or Al 2 O 3, containing,
    The symbols m, x and y indicating the composition molar ratio in the formula contained in the main component are
    1.005 ≦ m <1.1,
    0 ≦ x ≦ 1.0,
    0 ≦ y ≦ 0.4,
    The ratio of the first subcomponent with respect to 100 moles of said main component are the in MgO or Al 2 O 3 in terms of, Ri 0.05-3 mol der,
    The thickness of the dielectric layer, der Ru ceramic electronic component below 2 [mu] m.
  2. The ceramic electronic component according to claim 1, wherein an average crystal grain size of the dielectric particles constituting the dielectric layer is 2 μm or less.
  3. The dielectric layer is further contain a glass component, the content of the glass component, with respect to 100 moles of the main component, the ceramic electronic according to claim 1 or 2 is 0.01 to 15 mol parts.
  4. The dielectric layer is further contain a second auxiliary component composed of an oxide of Mn, the ratio of the second subcomponent with respect to 100 moles of said main component are the in terms of MnO, 0-4 mole (note that 0 The ceramic electronic component according to any one of claims 1 to 3 , wherein the ceramic electronic component is not included.
  5. The dielectric layer is an oxide of R (wherein R is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu). A third subcomponent consisting of at least one selected) and / or a fourth subcomponent consisting of an oxide of V, Nb, W, Ta, Mo,
    In the case of containing the third subcomponent, the ratio of the third subcomponent to 100 mol of the main component is 6 mol or less in terms of R element,
    The ratio of the said 4th subcomponent with respect to 100 mol of said main components in the case of containing the said 4th subcomponent is 2 mol or less in conversion of the metal element in an oxide, Any one of Claims 1-4. Ceramic electronic components.
  6. A method of manufacturing a ceramic electronic component according to any one of claims 1 to 5
    Preparing a dielectric material that will constitute the dielectric layer after firing;
    Firing the dielectric material, and
    When preparing the dielectric material, as the material of the first subcomponent, an oxide of A (wherein symbol A is one or more elements selected from Mg and Al) and / or A after firing The compound to be an oxide is used without previously reacting with other components that constitute the dielectric material,
    A method for producing a ceramic electronic component comprising firing in the form of an oxide of A alone and / or in the form of a compound alone which becomes an oxide of A after firing.
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