JP2646734B2 - Ceramic capacitor and method of manufacturing the same - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention generally functions as a capacitor to absorb low-voltage noise and high-frequency noise, while providing a varistor function when a high voltage such as a pulse or static electricity enters. The present invention relates to a ceramic capacitor which exhibits semiconductor characteristics, protects semiconductors and electronic equipment from abnormal voltages such as noise, pulses, static electricity, etc. generated in electronic equipment, and furthermore, their characteristics are always stable with respect to temperature and a method of manufacturing the same. is there.

2. Description of the Related Art In order to realize multifunctional, light, thin and compact electronic devices,
Semiconductor devices such as C and LSI are widely used, and accordingly, the noise immunity of devices is decreasing. In order to ensure the noise immunity of such electronic devices, various ICs and LSIs
In such power supply lines, film capacitors, multilayer ceramic capacitors, semiconductor ceramic capacitors and the like are used as bypass capacitors. However, these capacitors exhibit excellent performance in absorbing low-voltage noise and high-frequency noise, but do not have the function of absorbing high-voltage pulses or static electricity.
When a pulse or static electricity enters, a major problem is that malfunction of equipment, destruction of a semiconductor, and destruction of a capacitor are caused. Therefore, for such applications, in addition to good noise absorption and stability over temperature and frequency, SrTiO ₃ based semiconductors have been developed as a new type of capacitor with high pulse tolerance and excellent pulse absorption. A grain boundary insulated semiconductor ceramic capacitor with a varistor function in a ceramic capacitor (hereinafter referred to as a ceramic capacitor with a varistor function) has been developed.
57-27001 and JP-A-57-35303. This ceramic capacitor with a varistor function normally absorbs low-voltage noise and high-frequency noise as a capacitor, but functions as a varistor when a high voltage such as a pulse or static electricity enters, and generates noise and pulse generated in electronic equipment. It has the feature of protecting semiconductors and electronic devices from abnormal voltage such as static electricity.
Its use is being increasingly expanded.

On the other hand, in the field of electronic components, lighter, thinner, smaller, and higher performance have been increasingly promoted, and even with this varistor function-equipped ceramic capacitor, demands for smaller size and higher performance have been increasing. However, since the conventional ceramic capacitor with a varistor function is of a single-plate type, if the size is reduced, the area of the electrode is reduced, and as a result, there is a problem that the capacity is reduced and the reliability is reduced. Therefore, as a solution to this, it is expected to expand to a lamination in which the electrode area can be reduced. However, the ceramic capacitor with varistor function, usually coated with oxide on the surface of the SrTiO ₃ based semiconductor device, since a step of insulating the grain boundary layer by thermal diffusion, BaTiO ₃ based layered ceramic generally used It has been considered that it is extremely difficult to form a multilayer capacitor with a varistor function (hereinafter, referred to as a multilayer ceramic capacitor with a varistor function) by firing at the same time as the internal electrodes as compared with the capacitor.

Therefore, as a method of solving the problem of co-firing, JP-A-54-53248 and JP-A-54-53250 are applied, and a ceramic paste with a large amount of organic binder is printed on a portion corresponding to an internal electrode. Then, this part forms a porous layer in the sintering process, and after sintering, a method of injecting a conductive metal into the porous layer under an appropriate pressure, or forming an internal electrode by a plating method or a melting method, A method for forming a multilayer ceramic capacitor with a varistor function has been developed and provided. However, these are quite difficult in terms of process and have not yet reached the level of practical use.

JP-A-59-215701 discloses a conductive paste in which a heat diffusion material capable of insulating a grain boundary layer is mixed on a raw sheet made of powder calcined in a non-oxidizing atmosphere. Printing and sintering in an oxidizing atmosphere, and furthermore, JP-A-63-219115 discloses that a pre-semiconductor powder is used as a main component, and an oxidizing agent and a glass component for forming an insulating layer thereon. There has been reported a method in which a molded body obtained by alternately laminating a raw sheet containing a mixed diffusing agent and internal electrodes is fired in air or an oxidizing atmosphere. However, in these methods, the sintering temperature is relatively low at 1000 to 1200 ° C., and sintering of the ceramic is difficult to occur, so that the crystal particles are hardly brought into surface contact, and the completed element has not reached a perfect sintered body. It has the disadvantage that the capacitance is low, the voltage nonlinearity index α, which is a typical characteristic of a varistor, is small, the varistor voltage is unstable, and the reliability is poor. Furthermore, in the latter JP-A-63-219115, since a glass component is added as an additive, a glass phase is precipitated at a crystal grain boundary, and the above-mentioned electric characteristics are easily deteriorated, and the reliability is poor. And has not reached the level of practical use.

As a patent for a multilayer varistor, Japanese Patent Publication No. 58-23921 has already proposed a multilayer voltage non-linear element using ZnO, Fe ₂ O ₃ , and TiO ₂ . However, since this element has almost no capacitance, it exhibits excellent performance against pulses with relatively high voltage and absorption of static electricity, but against noise with low voltage below the varistor voltage and high frequency noise. Have the problem that they show little effect.

Problems to be Solved by the Invention Until now, various compositions and manufacturing methods have been developed and provided for multilayer ceramic capacitors with a varistor function, but as described above, in any case, there are problems in terms of process and completed devices. Has a point and has not reached a practical level. Therefore, development of a new composition and a new manufacturing method for the multilayer ceramic capacitor with a varistor function is expected.

The present invention has been made in view of such a point, and usually functions as a capacitor to absorb low-voltage noise and high-frequency noise, and when a high voltage such as a pulse or static electricity enters, a varistor function is provided. Sr _(1-x) Ba _x TiO ₃ (which has the characteristics that are always stable with respect to temperature and enables the simultaneous firing of ceramic capacitor material and internal electrode material However, 0 <x ≦
0.3) as a main component and a method for manufacturing the same.

Means for Solving the Problems To solve the above problems, the present invention provides
Sr _(1-x) Ba _x TiO ₃ containing excess Ti so that the molar ratio of _(1-x) Ba _x and Ti is 0.95 ≦ Sr _(1-x) Ba _x /Ti<1.00 (however,
0 <x ≦ 0.3), Ta ₂ O ₅ , Nb ₂ O ₅ , V ₂ O ₅ , W ₂ O ₅ , Dy ₂ O ₃ , Nd
₂ O ₅ , Y ₂ O ₃ , La ₂ O ₃ , CeO ₂
5 to 2.0 mol%, Mn and Si converted to MnO ₂ and SiO ₂ respectively, and a total amount of 0.2 to 5.0 mol%, and Na ₂ SiO ₃ to 0.05 to 2.0 mol%
A ceramic capacitor is provided. Further, the present invention, the molar ratio of Sr _(1-x) Ba _x and Ti is 0.95 ≦
Sr containing excess Ti so that Sr _(1-x) Ba _x /Ti<1.00
r _(1-x) Ba _x TiO ₃ (where 0 <x ≦ 0.3), Nb ₂ O ₅ , Ta ₂ O ₅ ,
_{V 2 O 5, W 2 O} 5, Dy 2 O 3, Nd 2 O 3, Y 2 O 3, La 2 O 3, and 0.05 to 2.0 mol% of at least one or more of the CeO _2, Mn and Si Each
0.2 to 5.0 mol% in total in terms of MnO ₂ and SiO ₂ and Na ₂ Si
The O ₃ in the ceramic made by including 0.05 to 2.0 mol%, the internal electrodes of the plurality of layers formed to reach the edges of these faces alternately, and providing the external electrodes to the opposite ends of the internal electrodes And a ceramic capacitor characterized by the following. Further, the present invention provides that the molar ratio of Sr _(1-x) Ba _x to Ti is
Nb is added to Sr _(1-x) Ba _x TiO ₃ (0 <x ≦ 0.3) containing excess Ti so that 0.95 ≦ Sr _(1-x) Ba _x /Ti<1.00.
_{At least one of 2} O ₅ , Ta ₂ O ₅ , V ₂ O ₅ , W ₂ O ₅ , Dy ₂ O ₃ , Nd ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , CeO ₂ is 0.05 ~ 2.0mol%, Mn and Si
Are converted to MnO ₂ and SiO ₂ respectively, and the total amount is 0.2 to 5.0 mol.
% And a mixed powder containing 0.05 to 2.0 mol% of Na ₂ SiO ₃ as a starting material, and pulverized, mixed,
After drying, a step of calcining in air or a nitrogen atmosphere, and after calcining, disperse the ground powder again in a solvent together with an organic binder into a raw sheet, and then put the internal electrode paste on the raw sheet. A process of printing (but not printing on the uppermost and lowermost raw sheets) so as to reach alternately facing edges, and laminating, pressing and crimping the printed raw sheets of the internal electrode paste Obtaining a molded body, then calcining the molded body in the air, calcining, calcining in a reducing or nitrogen atmosphere, calcining, reoxidizing in air, and reoxidizing. And a step of applying and baking external electrode paste on both ends where the internal electrodes are exposed, and a method for manufacturing a ceramic capacitor. And the internal electrodes are An, Pt, Rh, Pd,
It is provided that it is formed by at least one kind of metal of Ni or an alloy or a mixture thereof. Further, the present invention provides that the external electrode is formed of at least one kind of metal among Pd, Ag, Ni, Cu, Zn or an alloy or a mixture thereof.

In general, in order to convert Sr _(1-x) Ba _x TiO ₃ into a semiconductor, it is necessary to carry out forced reduction or to add a semiconducting accelerator and to fire in a reducing atmosphere. However, this alone may not make the progress of semiconducting depending on the type of semiconducting accelerator. Therefore, from the stoichiometry of Sr _(1-x) Ba _x TiO ₃ , Sr _(1-x) B
a _x excess (hereinafter referred to as excess A-site), or when the Ti-rich, increases lattice defects in the crystal, semiconductor is promoted. Further, Nb ₂ O ₅ , Ta ₂ O ₅ , V ₂ O ₅ , W ₂ O ₅ , Dy ₂ O ₃ , Nd ₂ O ₃ ,
Addition of Y ₂ O ₃ , La ₂ O ₃ , and CeO ₂ (hereinafter, referred to as a first component) promotes the formation of a semiconductor by atomization control.

Next, MnO ₂ and SiO ₂ (the second component to be obtained) are indispensable substances for forming a laminated structure in the firing process, and even if one of them is lacking, the action is not exhibited. As described above, it has been considered that it is difficult to manufacture a multilayer ceramic capacitor with a varistor function until now. The first reason is that the ceramic capacitor material having a varistor function and the internal electrode material have different functions and properties in the firing process and the re-oxidation process. That is, the former material requires firing in a reducing atmosphere in the firing process, but at this time, since the latter material is formed of a metal, it absorbs H ₂ gas in the reducing atmosphere and expands. Further, the latter material is oxidized to a metal oxide during the reoxidation process in the air, and has a function and a property of shielding the reoxidation of the former material.

Also, as the second reason, in order to form the former material as a ceramic capacitor element with a varistor function, after firing in a reducing atmosphere to form a semiconductor, a high-resistance metal oxide (MnO ₂ , CuO ₂ , Bi ₂ O ₃ , Co ₂ O _3, etc.), and re-oxidize in air to selectively diffuse the grain boundaries to make them insulating, that is, a surface diffusion step is required. However, in an element having a structure alternately laminated with the internal electrode material, diffusion of metal oxide is technically difficult.

Then, the present inventors invented the following as a result of research.

First, in addition to the addition of the first component to Sr _(1-x) Ba _x TiO ₃ in excess of Ti, in the material composition to which the second component is added, after firing in a reducing atmosphere, It has been found that a ceramic capacitor with a varistor function can be easily formed simply by re-oxidizing in air without applying such a high-resistance metal oxide as described above. This is because, during the sintering process, excessive Ti and the added second component form a liquid phase of MnO ₂ -SiO ₂ -TiO _{2 at} low temperature to promote sintering, and at the same time, dissolve in the grain boundary and segregate. Will do. Then, when this is reoxidized in the air, the MnO ₂ —SiO ₂ —TiO ₂ system segregated at the grain boundaries is insulated and easily becomes a ceramic capacitor with a varistor function having a grain boundary insulating structure. Furthermore,
It has also been found that an excessive amount of Ti can suppress oxidation and diffusion of the internal electrode. Therefore, in the present invention, Sr _(1-x) Ba _x TiO ₃ in excess of Ti is used for these reasons.

Second, it has been found that the material composition obtained by adding the second component to Sr _(1-x) Ba _x TiO ₃ in excess of Ti can be converted into a semiconductor by sintering in a nitrogen atmosphere in addition to the reducing atmosphere. . this is,
As described in the first reason, in order to form a liquid phase at a low temperature, the added Mn acts as an atomization control agent in addition to forming a liquid phase. At this time, the valence of Mn atoms is +2, +4. It is considered that, due to the effect of being unstable electronically, the sinterability is improved and a semiconductor can be easily formed even in a nitrogen atmosphere.

Third, if the molded body after degreasing is calcined in the air in advance, the internal electrodes of the completed multilayer ceramic capacitor with a varistor function are cut, delaminated, cracked, and so on.
It has been found that the occurrence of various problems such as a reduction in sintering density is suppressed as much as possible, and that the electrical characteristics and reliability are significantly improved.

As described above, when such a viewpoint is sufficiently considered, it is possible to easily manufacture a multilayer ceramic capacitor having a varistor function by simultaneously firing a ceramic capacitor material having a varistor function and an internal electrode material.

Further, Na ₂ SiO ₃ (hereinafter, referred to as a third component) contains MnO ₂
Acts as a carrier that uniformly diffuses the liquid phase of -SiO ₂ -TiO ₂ into the grain boundaries, and sharply forms the boundary between the semiconductor crystal and the high-resistance grain boundaries, resulting in temperature characteristics of capacitance and varistor voltage. Is to improve.

Examples Hereinafter, the present invention will be described specifically with reference to examples.

(Example 1) First, Sr _0.8 having an average particle diameter of 0.5 μm or less and a purity of 98% or more.
TiO ₂ was added to the raw material powder of Ba _0.2 TiO _3, and the powder having an adjusted Sr _(1-x) Ba _x / Ti ratio (hereinafter referred to as A / B ratio ₎ was added to the following Tables 1 to
As shown in Table 5, the first component Nb ₂ O ₅ , the second component MnO ₂ , SiO
₂ (however, MnO ₂ and SiO ₂ to be added are assumed to be equimol%) by variously changing the addition amount of Na ₂ SiO ₃ as the third component to 0.5 mol
l% and mixed. Thereafter, the mixed powder is wet-pulverized and mixed by a ball mill or the like, dried, and calcined at 600 to 1200 ° C. in air. After calcining, the average particle size is 0.5 μm.
Pulverization was again performed as described below, and this was used as a starting material for a laminated ceramic capacitor with a varistor function. The starting material of the fine powder was dispersed in a solvent together with an organic binder such as butyral resin to form a slurry, which was formed into a raw sheet having a thickness of about 50 μm by a doctor blade method and cut into a predetermined size. Next, as shown in FIG. 1, an internal electrode paste 2 made of Pd was screen-printed on the raw sheet 1 obtained as described above according to a predetermined size. As is clear from FIG. 1, the inner electrode paste 2 is not printed on the uppermost and lowermost raw sheets 1. At this time, the internal electrode paste 2 printed on the raw sheet 1 to be laminated in the middle is
As is well known, printing was performed so as to reach alternately opposite edges. Then, a plurality of raw sheets 1 were laminated in the printed direction of the internal electrode paste 2 and pressed and pressed. Next, degrease at 400 ° C in air, and
Calcination was performed at 50 ° C. Then 1250-13 in a reducing atmosphere
Fired at 50 ° C. After this calcination, it was reoxidized in air at 900 to 1250 ° C.

Thereafter, as shown in FIG. 2, an external electrode paste made of Ag is applied to both ends exposing the internal electrodes 2a and baked in air at 800 ° C. for 15 minutes to form the inside of the grain boundary insulating semiconductor ceramic. Then, a multilayer ceramic capacitor 4 with a varistor function was obtained in which a plurality of layers of internal electrodes 2a were provided so as to alternately reach the ends, and external electrodes 3 were provided at both ends of the internal electrodes 2a.

The shape of the multilayer ceramic capacitor with a varistor function in the present embodiment is a 5.5 type of 5.70 × 5.00 × 2.00 mm ³ , which is formed by laminating 10 effective layers on which internal electrodes are formed. FIG. 3 shows a manufacturing process of the present invention.

Various electrical characteristics such as capacitance, tanδ, varistor voltage, voltage non-linear exponent α, series equivalent resistance value ESR, capacitance temperature change rate, and varistor voltage temperature coefficient of the multilayer ceramic capacitor with varistor function thus obtained are described. Are also shown in Tables 1 to 15. However, for each condition such as firing at this time, calcining in air is 1200 ° C for 2 hours,
Firing in a reducing atmosphere of N ₂ : H ₂ = 99: 1 is performed at 1300 ° C for 2 hours.
Reoxidation was performed at 1100 ° C for 1 hour.

The following measured values are described for various electric characteristics.

◇ Capacity C is a value at a measurement voltage of 1.0 V and a frequency of 1.0 KHz.

◇ Varistor voltage V _0.1mA is the value at measurement current 0.1mA.

◇ The voltage non-linear index α was calculated from the values at the measured currents of 0.1 mA and 1.0 _{mA according to} the formula α = 1 / log (V _{1.0 mA} / V _{0.1 mA} ).

◇ Series equivalent resistance value ESR is the resistance value at the resonance point at a measurement voltage of 1.0V.

◇ Capacity temperature change rate (ΔC / C) is the value between -25 ℃ and 85 ℃.

◇ The varistor voltage temperature coefficient (ΔV / V) is the value between 25 ° C and 50 ° C.

Next, Tables 1 to 15 will be described. These tables show that the A / B ratio of Sr _0.8 Ba _0.2 TiO ₃ and the MnO _{2 of} the second component
And the amount of SiO ₂ added.

Here, the sample number is marked with * for comparison.
It is outside the scope of the present invention. In other words, these sintered devices have a small capacitance, a small voltage non-linear index α representing varistor characteristics, and a large series equivalent resistance value ESR, so that they absorb low-voltage noise and high-frequency noise as capacitors. Function and the function of absorbing high voltage such as pulse and static electricity as a varistor at the same time. Furthermore, the capacitance temperature change rate and the varistor voltage temperature coefficient are large, and the reliability and electrical characteristics affect the temperature. It is easy to receive. Therefore, these samples are not suitable as ceramic capacitors with a varistor function for protecting semiconductors and electronic devices from abnormal voltages such as noise, pulses, and static electricity generated in the electronic devices. On the other hand, the other sample numbers have a large capacitance, a large voltage non-linear index α, and a small series equivalent resistance value ESR, so they function to absorb low-voltage noise and high-frequency noise as capacitors. And the pulse as a varistor,
It has both functions of absorbing high voltage such as static electricity at the same time, has a small capacitance temperature change rate and a small varistor voltage temperature coefficient, and has a characteristic that its reliability and electric characteristics are hardly influenced by temperature. Therefore, these samples are suitable as ceramic capacitors with a varistor function to protect semiconductors and electronic devices from abnormal voltages such as noise, pulses, and static electricity generated in the electronic devices.

Here, in the present invention, the A / B ratio of Sr _0.8 Ba _0.2 TiO ₃ is specified because, when the A / B ratio is larger than 1.00, the A site becomes excessive and the liquid phase of the MnO ₂ —SiO ₂ TiO ₂ system Is difficult to form, so that it is difficult to form a grain boundary insulating structure, and the internal electrodes are oxidized or diffused, and as a result, electrical characteristics and reliability are reduced. On the other hand, if the A / B ratio is less than 0.95, the sintered body becomes porous, and the sintered density decreases. Further, the average particle size of the starting material for the multilayered varistor function-equipped ceramic capacitor is specified to be 0.5 μm or less,
If it is larger than μm, the powder will agglomerate when it is made into a slurry, the sintered density of the resulting sintered body element will be small, and it will be difficult to turn it into a semiconductor.

Next, the total addition amount of MnO ₂ and SiO ₂ of the second component is specified because the addition effect of MnO ₂ -SiO _2-is not obtained if the addition amount of these second components is less than 0.2 mol%. Because it is difficult to form a TiO ₂ -based liquid phase, it is difficult to have a grain boundary insulating structure,
This is because the electrical characteristics and the sintered density are reduced. On the other hand, the second
If the amount of the component exceeds 5.0 mol%, the amount of the high-resistance oxide segregated at the grain boundary increases and the electrical characteristics deteriorate.

Furthermore, the molded body after degreasing is previously heated to 600 to 1250 ° C in air.
Calcination is the most important step in the method of manufacturing a multilayer ceramic capacitor with a varistor function of the present invention,
The electrical characteristics and reliability of the multilayer ceramic capacitor with a varistor function obtained as a result of this process are almost determined. The purpose of this process is to strengthen the adhesion between the ceramic capacitor material with varistor function and the internal electrode material,
Further, it is the control of the average particle size of the completed multilayer ceramic capacitor with a varistor function.

Here, the reason why the calcining temperature in the air is set in the range of 600 to 1250 ° C. is that if the calcining temperature is lower than 600 ° C., the effect cannot be obtained. On the other hand, if the calcination temperature exceeds 1250 ° C, sintering of the ceramic capacitor material with a varistor function proceeds. When firing in a reducing or nitrogen atmosphere in this state, stress concentration due to rapid shrinkage occurs in the sintered body, and the resulting multilayer ceramic capacitor with a varistor function causes various problems such as delamination and cracking. Will be.

When Ni is used as the internal electrode material, sintering of the former ceramic capacitor material and oxidation of the Ni internal electrode material occur, and then the sintered body and Ni react, and the diffusion of Ni proceeds.
In the resulting multilayer ceramic capacitor with a varistor function, various problems such as internal electrode breakage, delamination, and cracking occur.

When calcination is performed at a high temperature exceeding 1250 ° C, MnO ₂ -SiO _2-
The liquid phase sintering of TiO ₂ system proceeds rapidly, and the grain growth is promoted, and the density of the sintered body and the packing density decrease remarkably.

Then, if firing in a reducing or nitrogen atmosphere,
Semiconductor conversion is unlikely to occur.

For this reason, electrical characteristics and reliability are significantly reduced.

Further, by adding Na ₂ SiO ₃ as the third component, the rate of change in capacitance with temperature and the temperature coefficient of varistor voltage are improved. That is, the added Na ₂ SiO ₃ becomes MnO
₂ -SiO ₂ -TiO ₂ system of liquid phase acts as a carrier to uniformly diffuse the grain boundary, grain boundary border of the semiconductor crystal and a high resistance is due to be formed sharp.

The multilayer ceramic capacitor with the varistor function obtained in this way has a larger capacity, and is excellent in temperature characteristics and frequency characteristics, as compared with the multilayer varistor reported in the above-mentioned Japanese Patent Publication No. 58-23921. In the former, the varistor material with excellent surge absorption is simply laminated, while the present invention has both a capacitor function with excellent noise absorption and a varistor function with excellent pulse and electrostatic absorption. A ceramic capacitor material having a varistor function having a function is laminated, and is completely different in function and purpose of use.

Example 2 From Example 1, it was found that the total addition amount of MnO ₂ and SiO ₂ as the second component was required to be 0.2 to 5.0 mol%.
Next, the addition ratio of MnO ₂ and SiO ₂ as the second component was changed variously, and the A / B ratio of Sr _0.8 Ba _0.2 TiO ₃ was 0.97,
The addition amount of Nb ₂ O ₅ as the first component was fixed at 1.0 mol%, and the addition amount of Na ₂ SiO ₃ as the third component was fixed at 0.5 mol%. A ceramic capacitor was manufactured. The results are shown in Table 16 below.

Explaining Table 16 above, as is clear from the measurement results, in order to manufacture a multilayer ceramic capacitor with a varistor function, both MnO ₂ and SiO ₂ are required, and even if one of them is missing, it has a varistor function. A multilayer ceramic capacitor cannot be manufactured. That is, only when both components are present, a liquid phase of MnO ₂ —SiO ₂ —TiO ₂ system is formed, dissolves and segregates at the grain boundary part, and when reoxidized, the MnO ₂ —SiO ₂ segregated at the grain boundary part is insulated. This is because the element easily has a grain boundary insulating structure.

Note that comparing electrical characteristics such as capacity, voltage nonlinearity index α, and ESR, it is preferable that MnO _{2 is} slightly excessive.

Example 3 Next, Nb ₂ O ₅ , Ta ₂ O ₅ , V ₂ O ₅ , W ₂ O ₅ , Dy ₂ O as the first component
₃ , Nd ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , in order to regulate the addition amount of the atomization control agent of CeO ₂ , this was changed variously, the A / B ratio of Sr _0.8 Ba _0.2 TiO ₃ was 0.97 The addition amount of the second component is 1.0 mol% of MnO _{2 and} 1.0 mol of SiO ₂
%, And the addition amount of Na ₂ SiO ₃ as the third component was fixed to 0.5 mol%, and a multilayer ceramic capacitor with a varistor function was manufactured in the same manner as in Examples 1 and 2.
The results are shown in Tables 17 to 25 below.

Referring to Tables 17 to 25, the addition amount of the first component is specified. As is clear from the measurement results, if the addition amount is less than 0.05 mol%, the addition effect cannot be obtained, and This is because it is difficult to cause the formation. On the other hand, if the total amount of the first component exceeds 2.0 mol%, the formation of a semiconductor is suppressed, desired electrical characteristics cannot be obtained, and the sintered density is further reduced.

It should be noted that the addition of Nb ₂ O ₅ and Ta ₂ O ₅ as the first component makes it possible to use other V ₂ O ₅ , W ₂ O ₅ , Dy ₂ O ₃ , Nd ₂ O ₃ , Y ₂ O ₃ , La _The electrical characteristics were slightly better than the case where ₂ O ₃ and CeO ₂ were added.

Further, with respect to the composition of the mixture of the first component, the electric characteristics were measured for some of the combinations, and as shown in Table 25, the results showed that there was almost no difference in the characteristics between the case where one kind was added and the case where one kind was added. It was not seen. However, also in this case, the addition of Nb ₂ O ₅ and Ta ₂ O ₅ was slightly better in electrical characteristics than the case where other components were added.

On the other hand, when the average particle size of the starting material is larger than 0.5 μm, the effect of the first component tends to be hardly obtained.
It was confirmed that it was necessary to suppress the thickness to 5 μm or less.

(Example 4) Next, in order to regulate the addition amount of Na ₂ SiO ₃ as the third component, this was changed variously, and the A / B ratio of Sr _0.8 Ba _0.2 TiO ₃ was set to 0.9.
7, the addition amount of the first component is Nb ₂ O ₅ 0.5 mol%, Ta ₂ O ₅ 0.5 mol%,
The addition amount of the second component was fixed at 1.0 mol% of MnO _{2 and} 1.0 mol% of SiO ₂ , and a multilayer ceramic capacitor with a varistor function was manufactured in the same manner as in the above-described embodiment. The result is the following 26th
It is described in the table.

As described in Table 26 above, the addition of the third component, Na ₂ SiO ₃ , improves the rate of change in capacitance with temperature and the temperature coefficient of varistor voltage. This is because the added Na ₂ SiO ₃ is MnO ₂ -S
This is because it acts as a carrier for uniformly diffusing the iO ₂ -TiO ₂ -based liquid phase into the grain boundary portion, and therefore the boundary between the semiconductor crystal and the high-resistance grain boundary is sharply formed. Here, the addition amount of the third component, Na ₂ SiO ₃ , is defined by the third component.
If the added amount of the component is less than 0.05 mol%, the effect of adding the component cannot be obtained, and the capacity temperature change rate and the varistor voltage temperature coefficient are hardly improved. On the other hand, the addition amount of the third component is 2.0 mol.
%, Na ₂ SiO ₃ acts as a carrier at the grain boundary
Is increased, as a result, the capacity and the voltage nonlinearity index α decrease, the series equivalent resistance value ESR increases, the firing density decreases, and the mechanical strength decreases.

In addition, Na ₂ O and SiO ₂ were used as additives for the third component Na ₂ SiO _3.
It is conceivable to use _two mixed additives. But,
When this mixed additive of Na ₂ O and SiO ₂ is used, Na ₂ O
Is a very unstable substance, so that Na ₂ O is easily decomposed during firing, and scatters and diffuses into the atmosphere. It was confirmed that partially ionized Na ⁺¹ ions migrated under a high temperature voltage load, and characteristic deterioration occurred. So, Na to Si
By adding the compound with O ₂ , it is possible to provide a compound that is stable in the grain boundaries without impairing the function of Na. Therefore, it was confirmed that Na ₂ SiO ₃ was always required as the third component.

Example 5 In each of the above examples, Sr _(1-x) Ba _x TiO ₃ (where 0 <x ≦
0.3), the case where Sr _0.8 Ba _0.2 TiO ₃ is used has been described, but for other cases of _x , A / B of Sr _(1-x) Ba _x TiO ₃
The ratio was 0.97, and the amount of the first component added was Nb ₂ O ₅ 0.5 mol%, Ta ₂ O ₅ 0.5
mol%, the amount of the second component MnO ₂ 1.0mol%, SiO ₂ 1.0mol
%, And the addition amount of Na ₂ SiO ₃ as the third component was fixed at 0.5 mol%, and a multilayer ceramic capacitor with a varistor function was manufactured in the same manner as in the above-described example. The result is
Described in Table 27.

Explaining the above Table 27, the reason that the range of Sr _(1-x) Ba _x TiO ₃ is defined is that when x exceeds 0.3, the Curie point of BaTiO ₃ appears, and the capacity temperature change rate and the varistor voltage temperature coefficient decrease. This is because capacitor characteristics and varistor characteristics become unstable with respect to temperature, and reliability and performance deteriorate.

(Embodiment 6) In each of the above embodiments, the case where Pd was used as the internal electrode was described. However, for other Au, Pt, Rh, and Ni, Sr _0,8 Ba
_0.2 TiO ₃ A / B ratio is 0.97, the amount of the first component is Nb ₂ O ₅ 0.5mo
l%, Ta ₂ O ₅ 0.5 mol%, the addition amount of the second component is MnO ₂ 1.0 mol%,
SiO ₂ 1.0 mol%, the addition amount of the third component Na ₂ SiO ₃ is 0.5 mol%
, And a multilayer ceramic capacitor with a varistor function was manufactured in the same manner as in the above example. The results are shown in Table 28 below.

As described in Table 28 above, Au, P
It was confirmed that at least one kind of metal among t, Rh, Pd, and Ni, or an alloy or a mixture thereof can be used, and that an effect can be obtained. However, when using Ni
Since the oxidation of Ni occurs at a relatively low temperature, the oxidation is suppressed by mixing Pd or using Sr _(1-x) Ba _x TiO ₃ with a slight excess of Ti.

As described above, in the embodiments of the present invention, some combinations are shown, but it has been confirmed that similar effects can be obtained with other combinations.

And in the example of the present invention, Ti excess Sr _(1-x) Ba _x TiO ₃
TiO ₂ was added to Sr _(1-x) Ba _x TiO ₃ to produce Ti, but Ti may be used in the form of carbonate, hydroxide, organic compound, etc., and the same effect can be obtained. Needless to say.

Further, in the examples of the present invention, Sr _(1-x) Ba _x Ti
It was used _{O 3, SrO, SrCO 3,} BaO, and BaCO _3, etc. TiO ₂ S
It is a matter of course that the same effect can be obtained even when the material prepared from r _(1-x) Ba _x TiO ₃ is used as a raw material powder.

Further, it goes without saying that the same effect can be obtained by using MnO ₂ and SiO ₂ as the second component in the form of these carbonates and hydroxides. However, it was confirmed that the use of MnCO _{3 provided a} finer particle size and was easier to decompose, so that a device with stable characteristics could be manufactured, which was suitable for mass production.

Next, in the above embodiment, the case where the baking is performed in a reducing atmosphere has been described, but this may be performed in a nitrogen atmosphere. However, when baking is performed in a nitrogen atmosphere, there is a surface where it is difficult to turn into a semiconductor.
(1450 ° C.) is preferable in terms of characteristics.

Further, in the above-described embodiment, the case where the calcination of the mixed powder is performed in the air has been described. However, it was confirmed that the same effect can be obtained by performing the calcination in the nitrogen atmosphere.

Further, in the above embodiment, the re-oxidation temperature was fixed at 1100 ° C.
It may be performed in a temperature range of 〜1250 ° C. But,
If reoxidation is performed at 1200 ° C. or more, care must be taken because not only the grain boundaries but also the crystal grains may be insulated unless the holding time at the maximum temperature is minimized. Also, in the case where Ni is used as the internal electrode, when reoxidizing at 1200 ° C. or higher, Ni may be oxidized unless the holding time is kept as short as possible.

In addition, although Ag was used as the external electrode in the above example, it was confirmed that similar effects could be obtained with other Pd, Ni, Cu, and Zn. That is, at least one of Pd, Ag, Ni, Cu, and Zn, or an alloy or a mixture thereof may be used as the external electrode. But Pd and Ag
Is difficult to make ohmic contact with the element and the varistor voltage has a slight polarity when used as an external electrode. In this case, however, there is no particular problem in basic performance.

As described above, the average particle size of the multilayer ceramic capacitor with a varistor function obtained by the method shown in the example is 2.0 to 3.0 μm.
It was about. Here, the calcining temperature of the molded body in air
When performed at a temperature higher than 1300 ° C., as described above, MnO ₂ —SiO ₂
-TiO ₂ -based liquid phase sintering progresses rapidly to promote grain growth,
The average particle size is approximately doubled. When the average particle size is increased in this manner, various problems such as a decrease in the sintering density, a decrease in the voltage nonlinearity index α, an increase in the series equivalent resistance value ESR, and variations in electric characteristics occur. The electrical characteristics and reliability are remarkably reduced, and are not suitable for practical use.

Further, in the above embodiments, a multilayer ceramic capacitor with a varistor function has been described. The characteristics and varistor characteristics were confirmed to be obtained.

As described above, the device obtained in this way has a large capacity, a large voltage nonlinearity index α, a small varistor voltage, a small series equivalent resistance value ESR, and excellent temperature characteristics, frequency characteristics, and noise characteristics. , Usually acts as a capacitor to absorb low voltage noise and high frequency noise,
On the other hand, when a high voltage such as a pulse or static electricity enters, it exhibits a varistor function, exhibits excellent responsiveness to abnormal voltages such as noise, pulses and static electricity, and its characteristics are always stable with temperature. Therefore, it is expected to replace conventional film capacitors, multilayer ceramic capacitors, and semiconductor ceramic capacitors. Furthermore, the multilayer ceramic capacitor with a varistor function of the present invention has a small size, a large capacity, and a high performance as compared with a conventional single-plate type ceramic capacitor with a varistor function, so that the application as a mounting component is greatly enhanced. It is expected.

Effect of the Invention As described above, according to the present invention, a ceramic capacitor with a varistor function having both a capacitor function and a varistor function can be obtained. As a function, the capacitor normally acts to absorb low-voltage noise and high-frequency noise, and when a high voltage such as a pulse or static electricity enters, it functions as a varistor. It has a function of protecting semiconductors and electronic devices from abnormal voltages such as pulses, static electricity and the like. And those characteristics are always stable with respect to temperature. Therefore, as applications, conventional film capacitors, as bypass capacitors for protection of ICs and LSIs used in electronic equipment,
Replaces multilayer ceramic capacitors, semiconductor ceramic capacitors, etc.

Replaces ZnO-based varistors used to prevent damage to equipment and malfunction of equipment due to static electricity, and to absorb dielectric load ON-OFF surges.

Application is expected, and the above-mentioned effects can be simultaneously exhibited by one element, and its application is large.

As described above, the reason that the multilayer ceramic capacitor with a varistor function can be easily manufactured in the present invention is that the ceramic capacitor material with a varistor function and the internal electrode material can be simultaneously fired. . The reason that simultaneous firing became possible is that the composition of MnO ₂ and SiO ₂ in addition to the addition of semiconductor components to SrTiO ₃ in excess of Ti, This is due to the fact that it can be easily converted to a grain boundary insulated semiconductor ceramic capacitor only by re-oxidation without passing through a process, and the present invention has the greatest feature in the process in this respect. .

In addition, the multilayer ceramic capacitor with a varistor function of the present invention is smaller, has a larger capacity, and has higher performance than conventional single-plate type ceramic capacitors with a varistor function. It can also be used as a high-density mounting element for video cameras, communication equipment, and the like.

Therefore, according to the present invention, it is possible to obtain an element which protects semiconductors and electronic devices from abnormal voltages such as noise, pulses and static electricity, and whose characteristics are always stable with respect to temperature. The effect is extremely large.

[Brief description of the drawings]

FIG. 1 is an exploded perspective view of a ceramic capacitor having a varistor function for explaining an embodiment of the present invention, and is a diagram for explaining shapes of a laminated raw sheet and an internal electrode paste printed thereon. FIG. 2 is a partially cutaway sectional view showing a multilayer ceramic capacitor with a varistor function obtained according to an embodiment of the present invention, and FIG. 3 is a view showing a manufacturing process of the multilayer ceramic capacitor with a varistor function for explaining the embodiment of the present invention. FIG. 1 ... raw sheet, 2 ... internal electrode paste, 2a ... internal electrode, 3 ... external electrode, 4 ... multilayer ceramic capacitor with varistor function.

Claims (7)

(57) [Claims] A ceramic is provided between electrodes, and the ceramic has a molar ratio of Sr _(1-x) Ba _x to Ti of 0.95 ≦ Sr _(1-x) Ba _x / Ti
Sr _(1-x) Ba _x TiO ₃ containing excess Ti so as to be <1.00
(However, 0 <X ≦ 0.3), Nb ₂ O ₅ , Ta ₂ O ₅ , V ₂ O ₅ , W ₂ O ₅ , Dy ₂
At least one of O ₃ , Nd ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , and CeO ₂ is 0.05 to 2.0 mol%, and Mn and Si are converted to MnO ₂ and SiO ₂ , respectively. and 0.2～5.0Mol% in an amount, a Na ₂ SiO ₃ 0.05~2.0m
ol% ceramic capacitor. A ceramic is provided between the electrodes, and the ceramic has a molar ratio of Sr _(1-x) Ba _x to Ti of 0.95 ≦ Sr _(1-x) Ba / Ti <
Sr _(1-x) Ba _x TiO containing excess Ti to be 1.00
₃ (However, 0 <X ≦ 0.3), Nb ₂ O ₅ , Ta ₂ O ₅ , V ₂ O ₅ , W ₂ O ₅ , Dy
_At least one of ₂ O ₃ , Nd ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , and CeO ₂ is converted to 0.05 to 2.0 mol%, and Mn and Si are converted to MnO ₂ and SiO ₂ respectively. and 0.2～5.0Mol% in total amount, the Na ₂ SiO ₃ 0.05~2.
A ceramic capacitor characterized in that a plurality of layers of internal electrodes are provided in a ceramic containing 0 mol% so as to extend to edges facing each other alternately, and external electrodes are provided on both ends of the internal electrodes. . 3. The ceramic capacitor according to claim 2, wherein the internal electrode is made of at least one of Au, Pt, Rh, Pd, and Ni, or an alloy or a mixture thereof. 4. The external electrode is made of at least one metal of Pd, Ag, Ni, Cu, Zn, or an alloy or mixture thereof.
The ceramic capacitor as described. 5. The method according to claim 1, wherein the molar ratio of Sr _(1-x) Ba _x to Ti is 0.95 ≦ Sr _(1-x) B
Sr _(1-x) Ba containing excess Ti so that a _x /Ti<1.00
_x TiO ₃ (where 0 <X ≦ 0.3), Nb ₂ O ₅ , Ta ₂ O ₅ , V ₂ O ₅ , W ₂ O
₅ , at least one of Dy ₂ O ₃ , Nd ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , and CeO ₂ is 0.05 to 2.0 mol%, and Mn and Si are converted to MnO ₂ and Si, respectively.
And 0.2～5.0Mol% in a total amount in terms of O _2, the Na ₂ SiO ₃ 0.05
2.02.0 mol% of a mixed powder of the composition as a starting material, crushing, mixing and drying the mixed powder, and then calcining in air or nitrogen atmosphere, and after calcination, pulverizing again The powder is dispersed in a solvent together with an organic binder in a solvent to form a raw sheet, and then the internal electrode paste is printed on the raw sheet so as to alternately reach opposite edges (however, the raw sheet of the uppermost layer and the lowermost layer has A step of laminating, pressing, and pressing the green sheet on which the internal electrode paste is printed to obtain a molded body, and thereafter, calcining the molded body in the air. The method has a step of firing in a reducing or nitrogen atmosphere, a step of re-oxidizing in air after firing, and a step of applying and firing an external electrode paste on both ends of the internal electrode exposed after re-oxidation. Of ceramic capacitors Method. 6. The method of manufacturing a ceramic capacitor according to claim 5, wherein the internal electrode is formed of at least one of Au, Pt, Rh, Pd, and Ni, or an alloy or a mixture thereof. Method. 7. The external electrode is made of at least one of Pd, Ag, Ni, Cu and Zn, or an alloy or mixture thereof.
The manufacturing method of the ceramic capacitor described in the above.