TW201728556A - Dielectric ceramic body tolerant to instantaneous high voltage resisting dielectric damage caused by the instantaneous potential exponential increase - Google Patents

Abstract

The present invention relates to a dielectric ceramic body tolerant to instantaneous high voltage, the dielectric ceramic body comprises a first main component BaTiO3 and a second main component ABO3, both main components satisfy the ratio formulation (A=Sr, Sr, Ca; B=Zr, Ti) of the general formula (100-x)BaTiO3-xABO3, wherein the second main component ABO3 is preferably SrZrO3 or CaZrO3, and at least one sub-component is further added for co-sintering, the formed dielectric ceramic body is a composite phase structure comprising co-existent orthorhombic and rhombohedral crystals; a capacitor made of this dielectric ceramic body has the effect of resisting dielectric damage caused by the instantaneous potential exponential increase, and the temperature capacitance is in compliance with EIA-X7R capacitor specification.

Description

Instantaneous high voltage dielectric ceramic body

The invention provides a transient high voltage resistant dielectric ceramic body, which has the anti-oxidation-reduction effect on the bauxite process, and can even withstand the high voltage impact of instantaneous potential difference change, and is prepared by the same. Multilayer ceramic capacitors also have excellent capacitance stability for temperature and comply with EIA-X7R capacitor specifications.

According to the Electronic Industries Association (EIA), capacitors are classified into ClassI temperature-compensated capacitors and Class II high-medium-capacity capacitors (as shown in the first figure) based on their different ranges of use and electrical characteristics. If the capacitor is classified as CaseII, it has a relatively high dielectric constant (K) and can even be easily fabricated into a capacitor with a high capacitance value. However, when any type of capacitor is used in the design of an electronic component circuit, the complex electric field signal will actively interfere with the components on the electronic circuit driven by voltage and electrical energy. Because capacitors have good insulation properties and can withstand high voltage fluctuations, capacitors are often added to the circuit as a protection device to absorb this sudden electronic signal. Specifically, if a commercially available capacitor product is observed, the product approval document will record the voltage limit that the capacitor product can withstand, but in common cases, even if the voltage limit described in the acknowledgment is not exceeded, the capacitor continues to fail. Return The reason is that the promised withstand voltage value measured at the time of shipment of the commercially available capacitor and the instantaneous voltage value generated by the working environment are different from each other. Taking the same measurement voltage as an example, when the instantaneous voltage rise rate is very rapid, especially when the DC current is used, the defects existing in the dielectric material of the capacitor are driven by the instantaneous high electric field energy to cause the dielectric collapse phenomenon.

Regarding defects in the dielectric material, regardless of the defect form or the defect concentration, it is generally affected by the material composition and the sintering process. For example, commercially available laminated ceramic capacitor products, based on manufacturing cost considerations, many manufacturers will choose to use the Base-Metal-Electrode (BME) for production. The low cost of the base metal electrode is a problem that the defect concentration of oxygen vacancies and free electrons increases after the sintering process is likely to occur in the manufacturing process, and even the reoxidation heat treatment after sintering through the reducing atmosphere cannot completely eliminate defects such as oxygen vacancies and free electrons. Defects can reduce the insulation properties of commercially available multilayer ceramic capacitor products and even reduce product reliability. Therefore, the prior art has gradually developed the problem of adding sub-components to improve the insulation properties, but the residual defects remaining inside the material cannot be completely overcome, so for transient high-voltage or high-energy shocks such as lightning strikes or surges, The failure of the capacitor product caused by it still suffers from no countermeasures. Furthermore, the capacitor can be used for lightning strike or anti-surge. It is common to connect a plurality of capacitors in series to each other, so as to jointly enhance the withstand capability of the potential rapid rise power, thereby making up for the insufficient resistance of the single capacitor to the instantaneous voltage capability. . However, when a plurality of capacitors are connected in series, any one of the single capacitors may fail, and then some current conduction between the individual capacitors is again induced. Therefore, how to improve the ability of the single capacitor to withstand transient high voltage becomes an important issue.

Moreover, the impact of an instantaneous high voltage or a high electric field may also cause a sudden increase in the ambient temperature in the electronic circuit system. If the capacitor is lucky enough to withstand the destruction of the instantaneous high voltage or In the event of electric breakdown, the capacitor may not be able to withstand the effect of high temperature on the attenuation of the capacitance value. Therefore, the problem to be solved should further include how to maintain the performance of the capacitor value to be mild or avoid violent fluctuations. However, as described above by the American Electronics Industry Association for the classification of capacitors, the Class I temperature-compensated capacitors and the Class II high-medium-value capacitors have been disclosed to those skilled in the art at the beginning of the intrinsic architecture, development goals, and scheme design. Capacitor systems do not have the best of both worlds, so if you want to develop a capacitor product that combines high-temperature capacitance performance with resistance to transient voltage damage, it is equivalent to launching a serious product cross-border challenge.

Approximate prior art, for example, Japanese Patent Laid-Open No. 2004-107200, which discloses a dielectric ceramic composition formulation which can be combined with a smelting metal process which uniformly forms M ₄ in the grain boundary phase during the sintering process. R ₆ O(SiO ₄ ) ₆ crystal precipitates (M is at least one selected from the group consisting of alkaline earth elements; R is selected from at least one of rare earth elements), and it is a key factor for improving resistance to voltage breakdown and temperature characteristics. Moreover, a few years later, another skill has been discovered, for example, the Republic of China Patent Publication No. 200846299, which is further improved by the technique disclosed in the aforementioned Japanese Patent Laid-Open No. 2004-107200, firstly, M ₄ R ₆ O ( The SiO ₄ ) ₆ composite oxide is converted into one of the constituent raw materials, and the sintering process is started by special blending of other auxiliary components. According to the literature, the product life shortage and product reliability of the aforementioned Japanese patent technology can be improved. problem. However, observing the above-mentioned prior art technical solutions for the M ₄ R ₆ O(SiO ₄ ) ₆ composite oxide, the only defect is the temperature and capacitance of the entire capacitor due to the essential characteristics of the precipitate-containing oxide due to the composition of the precipitate. The performance of the change can only reach the EIA-X5R standard level, there is no way to make further breakthroughs. In other words, the prior art only hints at the severe cross-border challenges of this product. It may be a feasible strategy to find the direction from the crystallized precipitates, but the skilled person in the field has to find another new type of crystal precipitate or new composition formula to be able to Further improve the capacitor product.

Therefore, how to develop a multilayer ceramic capacitor when subjected to the impact of instantaneous high voltage or high energy, without causing the dielectric collapse problem, is the direction that the relevant manufacturers engaged in this industry are eager to study and improve.

Therefore, in view of the above problems and shortcomings, the inventors have collected relevant information, evaluated and considered through multiple parties, and have accumulated many years of experience in the industry to continuously design and resist the resistance of such composite phase structures. Instantaneous high voltage dielectric ceramic body. In addition to its good resistance to high voltage, it is also resistant to dielectric breakdown caused by sudden increase in power or potential, and has temperature and capacitance stability in accordance with EIA-X7R capacitor specifications.

The invention relates to a transient high-voltage dielectric ceramic body, the composition of which is formed by a plurality of different main components and at least one auxiliary component being sintered together, wherein the two main components are respectively the first main component BaTiO ₃ , The two main components ABO ₃ (A is selected from any group of elements consisting of Ba, Sr, Ca; B is selected from Zr or Ti elements), and the molar numbers of the two main components are in accordance with the formula (100-x) The formulation ratio of BaTiO ₃ -xABO ₃ (x=0.1~30), and at least one accessory component added is also referred to as the first subcomponent, such as magnesium oxide MgO or manganese carbonate MnCO ₃ . After sintering to form a dielectric ceramic body, the dielectric ceramic body is detected by XRD crystal structure diffraction and found to contain a composite perovskite structure of Tetragonal Crystal and Orthorhombic Crystal. In short, the dielectric ceramic body will be sintered to form another composite phase structure containing special diffraction peaks under the combination of special principal components and subcomponents.

In the aforementioned transient high voltage dielectric ceramic body, the second main component ABO _{3 is} preferably SrZrO ₃ or CaZrO ₃ . When fabricated into a multilayer ceramic capacitor and subjected to different electrical measurements, if two different DC voltage rise rates of 200Vdc/s (differential measured dielectric strength, BDV for short) and 6000Vdc/s (measured dielectric strength) are further observed , abbreviated as BDV _H ) test results, it can be found that the presence of tetragonal crystals and rhombohedral crystals in the dielectric ceramics, the capacitor's insulating group characteristics have been significantly improved, the most special BDV _H test results even show that the capacitor has an instant resistance Excellent effect of high voltage. In addition, the electrical measurement results also show that as the content of SrZrO ₃ or CaZrO ₃ increases, the dielectric loss value gradually decreases, which can effectively prevent the internal energy from being converted into thermal energy consumption, so that the internal temperature of the capacitor does not occur instantaneously. A dramatic increase in the situation, which in turn causes the internal electrodes of the base metal to be burned or unpredictable heat exhaustion.

In the above-mentioned instant high-voltage dielectric ceramic body, the number of moles of the second main component ABO ₃ is controlled in the range of 0.1 to 30 mTorr, and the preferred range is 0.1 to 15 m. If it exceeds 30 m, the rhombohedral crystal in the dielectric ceramic body will disappear, which in turn affects the desired technical effect.

The transient high voltage dielectric ceramic body, wherein the first component is selected from the group consisting of MgO, ZnO, CuO, GeO, FeO, NiO, MnCO ₃ or CoCO ₃ when the accessory component is the first component. Any one. The metal ions contained in the first subcomponent are substituted for Ti ⁴⁺ or Zr ⁴⁺ by acceptor doping, thereby providing an anti-reduction atmosphere.

The transient high voltage dielectric ceramic body, wherein the auxiliary component may further comprise a second auxiliary component, and the second secondary component is selected from the group consisting of GaO ₃ , Cr ₂ O ₃ , Sc ₂ O ₃ , La ₂ O ₃ , Nd ₂ a trivalent ion oxide composed of O ₃ , Pm ₂ O ₃ , Sm ₂ O ₃ , Eu ₂ O ₃ , Gd ₂ O ₃ , Dy ₂ O ₃ , Er ₂ O ₃ , Tm ₂ O ₃ and Yb ₂ O ₃ Any of the groups. The second subcomponent can reduce the oxygen vacancies generated during the sintering process of the reducing atmosphere, so that the insulation resistance value and product reliability are improved. However, when the amount added is too large, the dielectric constant may be lowered, so it is not preferable to add too much. Further, a third auxiliary component may be further added, and the third auxiliary component is a Si-containing oxide having a low melting point and can be used as a sintering aid, such as BaSiO ₃ , CaSiO ₃ and (Ba _0.6 Ca _0.4 )SiO ₃ groups. Any one. This can reduce the sintering temperature of the dielectric ceramic body and help the ion diffusion, and can also shorten the powder spacing by the physical action of the high temperature liquid phase, thereby eliminating the formation of pores. Otherwise, the sintering temperature is too high, and in addition to increasing the manufacturing cost, it is even easy to cause damage to the internal electrodes of the capacitor.

The above-mentioned instant high-voltage dielectric ceramic body, wherein any one of the sub-component molar numbers is between 0.1 and 7.0 m, and the preferred range is 0.1 to 3.0 m. When the amount is too large, the stability of the TCC temperature-capacitance curve may be unexpectedly deviated from the EIA-X7R specification, so special attention should be paid.

Overall, the dielectric ceramic body resistant to transient high voltage of the present invention has the following advantages:

(1) The capacitor 1 made of the dielectric ceramic body 11 is capable of withstanding a high electric energy shock caused by a rapid rise in power potential for a short period of time.

(2) The ceramic capacitor 1 made of the dielectric ceramic body 11 can avoid dielectric breakdown caused by an instantaneous lightning strike or a surge, and improve the high voltage resistance of the ceramic capacitor 1.

(3) The capacitor 1 prepared by the invention can combine the advantages of resistance to transient voltage damage and capacitor specifications conforming to EIA-X7R.

(4) The dielectric ceramic material of the present invention has good resistance to reduction and sintering, and is commercially competitive with the BME process.

1‧‧‧Ceramic capacitors

11‧‧‧Dielectric ceramic body layer

12‧‧‧Internal electrode layer

121, 122‧‧‧ internal electrodes

13‧‧‧External electrode

The first figure is a chart of the American Electronic Industry Association capacitor Class II specification.

The second drawing is a side sectional view of a multilayer ceramic capacitor according to an embodiment of the present invention.

The third figure is a preparation flow chart of an embodiment of the present invention.

The fourth figure is a schematic diagram of the capacitance of the preferred embodiment of the present invention for DC bias attenuation.

Figure 5 is an X-Ray diffraction pattern of a preferred embodiment of the invention.

The sixth figure is the component and detection data (1) of the embodiment of the present invention.

The seventh figure is the composition and detection data (2) of the embodiment of the present invention.

In order to achieve the above objects and effects, the technical means, the structure, the method of the implementation, and the like, which are used in the present invention, are described in detail in the preferred embodiments of the present invention.

Please refer to the second, third, fourth, fifth, sixth and seventh figures, which are respectively a side cross-sectional view, a preparation flow chart, and a schematic diagram of the capacitance of the preferred embodiment for DC bias attenuation, X. - Ray diffraction pattern, composition of the examples and test data (1) and the composition of the examples and test data (2).

As can be clearly seen from FIG. 2, when the dielectric ceramic body resistant to transient high voltage of the present invention is fabricated as the multilayer ceramic capacitor 1 of the embodiment, the composition of the dielectric ceramic body layer 11 is composed of a plurality of different principal components and The subcomponents are sintered, wherein the subcomponents have a molar number of 0.1 to 7.0 m, and the two main components are the first main component BaTiO ₃ and the second main component ABO ₃ (A=Ca, Sr, Ba; B = Zr, Ti), wherein, means of ABO ₃ SrZrO ₃ or CaZrO ₃ powder, or the powder mixture SrZrO ₃ and CaZrO ₃ according to an embodiment of the present invention, and two kinds of number of moles of the main component meet The formula ratio of the formula (100-x) BaTiO ₃ -xABO ₃ is such that the x series is between 0.1 and 30 m. When the dielectric ceramic body layer 11 is detected by an XRD diffractometer, it is found that the dielectric ceramic body layer 11 has a composite phase perovskite structure containing both tetragonal and rhombohedral crystals, and the diffraction results of the examples are as shown in FIG. . According to the X-Ray crystal structure diffraction analysis map (XRD) of the embodiment shown in FIG. 5, the dielectric ceramic material system formed by sintering according to the formula of (100-x) BaTiO ₃ -xABO ₃ is compared with The material formulation is only a single main component BaTiO ₃ with obvious crystal structure difference. (100-x) BaTiO ₃ -xABO ₃ dielectric ceramic material system shows a composite phase structure of tetragonal phase BaTiO ₃ and rhombohedral phase ABO ₃ (A = Ca, Sr, Ba; B = Zr, Ti), Or otherwise called a two-phase structure.

Further, if the embodiments are prepared as a multilayer ceramic capacitor and subjected to electrical measurement, the results can be arranged according to different composition components, such as the sixth and seventh figures, wherein the electrical measurement includes: through the inductance The capacitance resistance measuring instrument (LCR meter) performs the TCC value and the loss factor (DF) with a frequency of 1kH or less and 1Vrms, and the insulation resistance (IR) with a high resistance meter of 250Vdc. 200Vdc/s (measured dielectric strength, referred to as BDV) and 6000Vdc/s (measured dielectric strength, referred to as BDV _H ) are measured to withstand transient voltage capability.

Please refer to the results of the sixth and fifth figures at the same time. When the composite perovskite structure of tetragonal and rhombohedral is present at the same time, the laminated ceramic capacitor 1 prepared by the composite ceramic capacitor 1 has a significant improvement in insulation resistance. Comparing the different voltage rates of 200Vdc/s and 6000Vdc/s, the BDV _H result of the fabricated multilayer ceramic capacitor even shows the effect of resisting transient high voltage, that is, the prepared multilayer ceramic capacitor 1 can resist the instantaneous power. Damage caused by high voltage or high potential. Specifically, when observing Examples 1 to 11 listed in the sixth figure, when the first subcomponent of the dielectric ceramic layer 11 is kept constant, BDV and BDV _H obtain good values as the number of moles of the second principal component increases. result. Further, after carefully observing the examples 1 to 8, the laminated ceramic capacitors were maintained at a temperature change rate of ±15% in the temperature range of -55 ° C to 125 ° C, which was in compliance with the EIA-X7R specification. In other words, when the dielectric ceramics of the embodiment have both a tetragonal and rhombohedral composite perovskite structure, the laminated ceramic capacitors have excellent product characteristics, and are resistant to transient high voltage and EIA-compliant. -X7R high temperature capacitor stability characteristics.

Further, Examples 1 to 10 also show that when the composite perovskite structure contained in the dielectric ceramic body layer 11 has an effect of suppressing dielectric loss, and with the second main component SrZrO ₃ or CaZrO ₃ Moule As the number increases, the dielectric loss will be smaller. Dielectric loss is a situation of energy conversion, and most energy losses are in the form of electrical energy conversion heat. In addition, the dielectric loss is the sum of the losses caused by the phase shift of the electric field (ie, the alternating electric field), and the dielectric loss is inversely proportional to the ability to withstand AC voltage. The destruction mechanism of the dielectric material under the alternating electric field is mostly the thermal collapse caused by the thermal energy, so the lower the dielectric loss, the better the resistance to the alternating electric field. For the laminated ceramics 1, the larger the dielectric loss, the more easily the internal temperature of the laminated ceramic capacitor 1 is drastically increased, and if the internal temperature cannot be rapidly transmitted to the external environment through the external electrode 13 formed of copper or nickel, The internal electrodes 121, 122 made of base metal may burn or melt at any time. In addition, the effect of the dielectric properties enhanced by the composite perovskite structure contained in the dielectric ceramic body layer 11 is not limited to this, according to the embodiments 1, 3, 6, 7, 8, and 9 listed in the fourth figure. 10 and 11, when the auxiliary component remains unchanged, as the number of moles of the second principal component increases, the capacitance value of the laminated ceramic capacitor 1 produced will increase the resistance to DC bias. For example, when the DC bias voltage reaches 1.5 V/um, the capacitance change rate attenuation of about -20.0% has occurred in the first embodiment and the third embodiment, but the capacitance changes of the embodiment 9, the embodiment 10, and the embodiment 11 are changed. The rate decay phenomenon is still maintained in the range of -5.0%, and in particular, the capacitance change rate of Embodiment 11 is maintained at almost 0%. If the trend of each curve in the fourth graph is observed, when the dielectric ceramic body layer 11 increases with the second main component, the laminated ceramic capacitor 1 can be applied to a stronger DC bias environment, and has good resistance to capacitance value attenuation. effect.

Further, in order to describe in detail the technical effects of the present invention, the electrical measurement results will be analyzed and described in sequence according to the embodiments listed in the sixth figure. First, observe the composition formula of each embodiment in the sixth figure. When the second principal component is between 0 and 30 mol%, the dielectric strength BDV measured at a lower voltage increase rate of 200 Vdc/s can reach 71 to 119 Vdc/μm. This result is quite good withstand voltage capability, especially when the content of the second main component is between 3 and 11 mol%, and the dielectric strength BDV is even higher than 100 Vdc/μm. It should be reminded that the chemical composition of Example 1 is only a single main component of BaTiO ₃ and a plurality of sub-components are added, which has 110 Vdc/μm at a boost rate of 200 Vdc/s, but the boost rate is increased to 6000 Vdc/s. At the same time, the dielectric strength is only 27Vdc /μm. The reason for the inductive method is that the XRD diffraction peak shows only a single perovskite crystal structure because it does not add any second main component, so it can not exert the resistance to instantaneous high voltage. Technical effects. If the situation of lightning strike or glitch occurs, the characteristics of Embodiment 1 may cause the variation of the dielectric strength value to be excessively large, and then it is easy to impact the cooperation between the electronic components in the electronic circuit and cause failure, so the prepared capacitor is not A stabilized capacitor that is expected to withstand transient high voltage rises as contemplated by the present invention. On the other hand, in the capacitor which is expected to resist the transient high voltage power, the dielectric ceramic body layer 11 is formed by adding a second main component of at least 0.1 mole or more and forming a composite of tetragonal and rhombohedral crystals after sintering. Perovskite structure. Taking Example 4 and Example 7 as an example, since it contains a specific proportion of the second main component, after sintering, the dielectric ceramic body layer contains both the presence of tetragonal and rhombohedral crystals, and the composite perovskite structure The values of the dielectric strength of BDV and BDV _H tend to be gentle, indicating that the sudden impact of instantaneous high voltage will not cause excessive fluctuations, and the capacitance temperature changes under the action of a plurality of sub-components are also in compliance with the EIA-X7R specification. Regardless of the instantaneous high voltage change or high temperature change environment, they will be more stable capacitor products from the perspective of product reliability.

Further, according to the results of the examples shown in the sixth figure, when the second principal component content is between 5 and 15 moles, the measured BDV _{H is} higher than 70 Vdc/μm, and the result is not limited to the second main. The ratio between the components SrZrO ₃ and CaZrO ₃ should be maintained at a fixed condition of 1:1. For example, when the total content of the second principal component is maintained at 5 moles in Examples 12 to 21, the ratio of SrZrO ₃ /CaZrO ₃ is arbitrarily changed from 0 to 1, and the result is still very good transient voltage resistance and EIA-compliant. X7R specification. However, if the number of CaZrO ₃ moles added in the second principal component is too high, the TCC temperature capacitance stability will begin to deteriorate. Taking Example 21 as an example, although having good BDV _H characteristics, the measured TCC value at a high temperature of 125 ° C approximates the -15% critical limit required by the EIA-X7R specification.

Referring to each embodiment of the seventh embodiment, the seventh figure selects the number of moles of the first principal component and the second principal component described in the fourth embodiment and maintains the fixed number, and then arbitrarily changes the addition amount of the plurality of different accessory components. And the ratio, the purpose is to further optimize the rate of change of TCC temperature capacitance curve in the range of -55 ~ 125 °C and adjust the insulation resistance under the stability of the composite perovskite structure. Taking the first subcomponents MgO and MnCO ₃ as examples, among them, MgO has a good effect on the rate of change of the stable TCC temperature capacitance curve in the range of -55 to 125 °C, and the specific results are as shown in Examples 22-28. The amount of MgO added gradually increased from 0.5 mol to 7.0 mol, and the change rate of the capacitance value at 125 ° C converges from -14.5% to -6.6% at the beginning. At the same time, as the amount of MgO added increases, the insulation resistance also gradually increases from 66.9 GΩ to 100.9 GΩ. Another first subcomponent MnCO ₃ , as shown in Examples 29 to 33, has the effect of improving temperature and capacitance stability and improving insulation resistance as the amount of addition increases.

Further, each of the examples described in the seventh embodiment is observed, wherein the added trivalent metal ion oxide such as the second subcomponents Y ₂ O ₃ and Ho ₂ O ₃ is usually produced by lowering the sintering atmosphere in the reducing atmosphere. Oxygen vacancies, so as the amount of addition increases, the insulation resistance also tends to increase, as shown in Example 31 and Examples 34-41. When the amount of Y ₂ O ₃ added is 1 mole, the insulation resistance is 68.7 GΩ. When the addition amount is increased to 1.5, 2, 3 and 5 mole, the insulation resistance is also increased to 68.6 GΩ, 82. 3GΩ, 124.4GΩ and 149.4GΩ. Therefore, the addition of the second subcomponent increases the insulation resistance characteristics, and the temperature stability of the TCC capacitor hardly causes too much fluctuation, but when the amount of addition is too large, the dielectric constant is lowered, so the composition is adjusted. It should be noted. Further, from Example 34 and Examples 39 to 41, it is understood that an effect of replacing atoms between trivalent ions such as Y ₂ O ₃ and Ho ₂ O ₃ occurs.

Further, each of the examples described in the seventh embodiment is further observed, in which a third subcomponent is added to promote sintering, and an oxide containing Si ions is mainly selected, for example, (Ba _0.6 Ca _0.4 )SiO ₃ . Taking Example 31 and Examples 42 to 45 as an example, if the composition formula only changes the addition amount of (Ba _0.6 Ca _0.4 )SiO ₃ and continues to be between 0.5 and 2 mole, the dielectric properties are not Any significant changes will occur. However, if the addition amount is as high as 4 mole, the stability of the TCC temperature capacitance curve gradually decreases, but still conforms to the EIA-X7R specification, as shown in Embodiment 45. According to the results of the various examples listed in the seventh figure, whether adding any one of the sub-components, it should be between 0.1 and 7.0 m, preferably 0.1 to 3.0 m, because when the amount is too large, Special attention may be paid to the fact that the stability of the TCC curve may gradually deviate from the EIA-X7R specification or cause other dielectric properties.

Referring to FIG. 3, a method for preparing a capacitor for a dielectric ceramic body according to an embodiment of the present invention may be performed according to the following steps, wherein:

(A01) adding a main component, which may be two main components, respectively being a first main component BaTiO ₃ and a second main component ABO ₃ . And simultaneously

(A02) Adding at least one accessory component, which is a subcomponent different from the main component.

(A03) Preparation of a slurry, which may be added with toluene, anhydrous alcohol, a plasticizer, a binder, a dispersant, and the like.

(A04) Scraper forming a raw metal strip.

(A05) Screen printing internal electrode layer.

(A06) Preparation of raw embryos, lamination, pressure equalization, cutting, and the like.

(A07) Burning off organic matter.

(A08) Sintering in a reducing atmosphere.

(A09) Reoxidation heat treatment.

(A10) An external electrode was prepared.

(A11) Electrical measurement.

The above steps (A01) and (A02), wherein the main component and the subcomponent powder are prepared by firstly using BaCO ₃ , CaCO ₃ , SrCO ₃ , TiO ₂ , Zr ₂ O ₅ and SiO ₂ as common solid phase synthesis methods. It is calcined at a high temperature of 900 ° C to 1300 ° C to form BaTiO ₃ , CaZrO ₃ , SrZrO ₃ , CaTiO ₃ , SrTiO ₃ and (Ba _0.6 Ca _0.4 ) SiO ₃ powder. Then all the raw materials BaTiO ₃ , CaZrO ₃ , SrZrO ₃ , CaTiO ₃ , SrTiO ₃ , (Ba _0.6 Ca _0.4 )SiO ₃ , MgO, MnCO ₃ , Y ₂ O ₃ , Ho ₂ O ₃ and Al ₂ O _{3 The} powder is uniformly mixed according to the sixth and seventh figures relative to the molar ratio.

In the foregoing step (A03), the components are mixed to prepare a ceramic slurry, and the dielectric ceramic powder prepared in each relative proportion is added to toluene, anhydrous alcohol, plasticizer, binder and dispersant, and then uniformly mixed.

In the foregoing step (A04), a ceramic green embryo strip having a thickness of 25 μm was prepared by a doctor blade method.

In the foregoing step (A05), the screen inner electrode layer is printed by means of screen printing. A silver (Ag), platinum (Pb), copper (Cu) or nickel (Ni) metal paste is applied to the ceramic green foil strip with a designed internal electrode pattern.

In the foregoing step (A06), the preparation of the raw embryo mainly refers to three processes of lamination, pressure equalization and cutting, and the ceramic green embryo strips printed with the internal electrode pattern are sequentially stacked, and then the hot water equalizing method is used. The raw embryonic strip is compressed tightly and cut into a previously designed laminated ceramic green embryo.

In the above step (A07), the organic matter is burned off, and the laminated ceramic green embryos are held in a pure N ₂ atmosphere at a temperature of 330 to 500 ° C (heating rate 2 ° C / min) for 6 to 20 hours to make each organic matter in the green embryo. Completely burned out.

In the foregoing step (A08), the reducing atmosphere sintering refers to placing the laminated ceramic green body after burning the organic matter in a reducing atmosphere consisting of 98% N ₂ -2% H ₂ and saturated water vapor of 35 ° C, at 1000 to 1400 ° C. (The heating rate was 3 ° C / min) The sintering procedure was carried out and the temperature was held for 2 hours.

In the foregoing step (A09), after the reoxidation heat treatment is completed for 2 hours, the temperature is lowered to a temperature range of 900 ° C to 1050 ° C (cooling rate 4 ° C / min) and in an oxygen pressure of 60 ppm to 150 ppm or an atmospheric atmosphere. An oxidative heat treatment is carried out, and then gradually lowered to room temperature to obtain a laminated ceramic cooked embryo.

In the foregoing step (A10), the external electrode system is prepared to expose the electrode paste on both sides of the mature embryo with an electrode paste slurry such as silver (Ag), copper (Cu), nickel (Ni) or tin (Sn). The temperature was raised to 800 ° C to 900 ° C in a pure N ₂ atmosphere (cooling rate 15 ° C / min) and then cooled to room temperature, thereby completing the preparation of the laminated ceramic capacitor sample.

According to the foregoing process steps, the multilayer ceramic capacitor of the embodiment of the present invention is prepared as shown in the seventh figure. The multilayer ceramic capacitor 1 includes a plurality of stacked dielectric ceramic body layers 11 and a plurality of internal electrode layers 12 stacked along the surface of each of the dielectric ceramic body layers 11, and the plurality of internal electrode layers 12 may include a plurality of internal electrodes 121, 122 are interdigitated and spaced apart from each other by a dielectric ceramic body layer 11. The outer electrodes 13 are respectively formed on the outer sides of the multilayer ceramic capacitors 1, and the external electrodes 13 are respectively connected to the inner electrodes 121 and 122, wherein the dielectric layers 11 are electrically conducted to the inner electrodes 121 and 122. The barrier then produces a dielectric effect. The plurality of internal electrodes 121 and 122 of the internal electrode layer 12 may be internal electrodes made of a metal such as silver (Ag), platinum (Pb), copper (Cu) or nickel (Ni), and the base metal process is multi-system. Nickel (Ni) or copper (Cu) is selected as the nickel internal electrode. The external electrodes 13 may be external electrodes made of a metal material such as copper (Cu), nickel (Ni) or tin (Sn).

Therefore, the present invention is mainly designed for a dielectric ceramic body resistant to transient high voltage, the dielectric ceramic system comprising a first main component BaTiO ₃ and a second main component ABO ₃ , the two main components conform to the general formula (100-x a formulation ratio of BaTiO ₃ -xABO ₃ and a second main component ABO ₃ , wherein the A is selected from any group consisting of Ba, Sr, and Ca, and the B is selected from the group consisting of Zr or Ti, and the second main component The component ABO _{3 is} preferably SrZrO ₃ or CaZrO ₃ , and further sintered by adding at least one accessory component, and the formed dielectric ceramic system contains a composite phase structure in which tetragonal crystal and rhombohedral crystal coexist at the same time, and can achieve resistance to transient potential The dielectric damage caused by the ascending power, while the temperature and capacitance performance also meets the capacitor specifications of the EIA-X7R. However, the above description is only the preferred embodiment of the present invention, and thus it is not intended to limit the scope of the present invention. Therefore, the simple modification and equivalent structural changes of the present specification and the drawings should be treated similarly. It is included in the scope of the patent of the present invention and is combined with Chen Ming.

In summary, the above-mentioned instant high-voltage resistant ceramic capacitor body can achieve its efficacy and purpose when implemented in practical applications, so the invention is an excellent research and development, and is an application requirement for the invention patent.提出 Submit an application in accordance with the law, and hope that the trial committee will grant this case as soon as possible to protect the inventor's hard work in research and development, and create a report. If there is any doubt in the trial committee, please do not hesitate to give instructions to the inventor, and the inventor will try his best to cooperate.

1‧‧‧Multilayer ceramic capacitors

11‧‧‧Dielectric ceramic body layer

12‧‧‧Internal electrode layer

121, 122‧‧‧ internal electrodes

13‧‧‧External electrode

Claims (10)

An instant high voltage resistant dielectric ceramic body comprising a first main component BaTiO ₃ and a second main component ABO ₃ , wherein the two main components conform to the general formula (100-x) BaTiO ₃ -xABO ₃ Formulation ratio (30≧x≧0.1; A is selected from any group of elements composed of Ba, Sr, Ca; B is selected from Zr or Ti elements), and further contains at least one accessory component, wherein The dielectric ceramic body defines a composite structure containing a tetragonal perovskite and a rhombohedral perovskite on X-ray diffraction analysis. The dielectric ceramic body resistant to transient high voltage according to claim 1, wherein the second principal component content is between 1.0 and 15.0 m. The dielectric ceramic body resistant to transient high voltage according to claim 2, wherein the second main component is SrZrO ₃ or CaZrO ₃ . The dielectric ceramic body resistant to transient high voltage according to claim 1, wherein the auxiliary component is a first subcomponent, and the subcomponent content is 0.1 to 7.0 m. The dielectric ceramic body resistant to transient high voltage according to claim 4, wherein the auxiliary component is selected from the group consisting of MgO, ZnO, CuO, GeO, FeO and NiO. The dielectric ceramic body resistant to transient high voltage according to claim 4, wherein the auxiliary component is MnCO ₃ or CoCO ₃ . The dielectric ceramic body resistant to transient high voltage according to claim 4, further comprising a second subcomponent, wherein the second subcomponent is selected from the group consisting of GaO ₃ , Cr ₂ O ₃ , Sc ₂ O ₃ , La ₂ O ₃ , Nd ₂ O ₃ , Pm ₂ O ₃ , Sm ₂ O ₃ , Eu ₂ O ₃ , Gd ₂ O ₃ , Dy ₂ O ₃ , Er ₂ O ₃ , Tm ₂ O ₃ and Yb ₂ O ₃ Form a group. The dielectric ceramic body resistant to transient high voltage according to claim 7 , further comprising a third auxiliary component selected from the group consisting of BaSiO ₃ , CaSiO ₃ and (Ba _0.6 Ca _0.4 )SiO ₃ groups. The dielectric ceramic body resistant to transient high voltage according to claim 4, further comprising a second subcomponent selected from the group consisting of BaSiO ₃ , CaSiO ₃ and (Ba _0.6 Ca _0.4 )SiO ₃ groups. The transient high voltage dielectric ceramic body according to any one of claims 2 to 9, wherein any one of the subcomponent contents is between 0.1 and 5.0 m.