TWI658026B - Biaryl derivative and medicine containing the same - Google Patents

Abstract

The invention relates to a dielectric ceramic body capable of withstanding transient high voltage. The dielectric ceramic system includes a first main component BaTiO ₃ and a second main component ABO _{3. The} two main components conform to the general formula (100-x) BaTiO _3- The formula ratio of xABO ₃ (A = Sr, Sr, Ca; B = Zr, Ti), wherein the second main component ABO _{3 is} preferably SrZrO ₃ or CaZrO ₃ , and further added with at least one secondary component for sintering to form The dielectric ceramic system contains a composite phase structure in which both tetragonal and rhombohedral crystals coexist. The capacitor made of this dielectric ceramic body has been tested to have a dielectric breakdown effect caused by instantaneous potential rise, and the performance of temperature capacitance It also meets the capacitor specifications of EIA-X7R.

Description

Dielectric ceramic body resistant to transient high voltage

The invention provides a dielectric ceramic body capable of withstanding transient high voltages. The dielectric ceramic body has an oxidation-reduction effect on a base metal process, and can even withstand high-voltage impact of transient potential difference changes. Multilayer ceramic capacitors also have excellent capacitance stability to temperature and meet EIA-X7R capacitor specifications.

According to the American Electronics Industry Association (EIA), capacitors are classified as Class I temperature-compensated capacitors and Class II medium- and high-dielectric capacitors (as shown in the first figure) according to the different use ranges and electrical characteristics of capacitors. If the capacitor is classified as Case II, it has a relatively high dielectric constant (K), and can even be easily made into a capacitor with a high capacitance value. However, when any kind of capacitor is used in the design of electronic component circuits, complex electric field signals will actively interfere with components on the electronic circuit under the driving of voltage and electrical energy. Capacitors have good insulation characteristics and can withstand high voltage fluctuations, so capacitors are often installed in the circuit as a protection device to absorb this sudden electronic signal. Specifically, if you look at commercially available capacitor products, the product approval document will record the voltage limit that the capacitor product can withstand, but the common situation is that the capacitor continues to fail even if the voltage limit recorded in the approval document is not exceeded. Return The nano-cause is caused by the fact that the promised withstand voltage value measured at the time of shipment from the factory and the instantaneous voltage value generated by the working environment are different from each other. Taking the same measured voltage as an example, when the instantaneous voltage rise rate is very fast, especially those who use direct current, the defects existing in the dielectric material of the capacitor will be driven by the instantaneous high electric field energy and then cause the dielectric collapse phenomenon.

Regarding defects in dielectric materials, regardless of the defect form or defect concentration, they are generally affected by the material composition and sintering process. For example, commercially available multilayer ceramic capacitor products, based on manufacturing cost considerations, many manufacturers will choose to use Base-Metal-Electrode (BME) for production. Low-cost base electrodes are cheap, but in the manufacturing process, defects such as oxygen vacancies and free electrons increase after sintering. Even if the reoxidation heat treatment after sintering through a reducing atmosphere cannot completely eliminate defects such as oxygen vacancies and free electrons, these Defects will reduce the insulation characteristics of commercially available multilayer ceramic capacitor products, and even reduce the reliability of the product. Therefore, the conventional technique has gradually developed the problem of adding auxiliary components to improve the insulation characteristics, but the residual sintering defects inside the material still cannot be completely overcome. Therefore, for transient high voltage or high energy impacts, such as lightning strikes or surges, The failure of capacitor products caused by it still has no countermeasures. In addition, capacitors can be used for anti-lightning or anti-surge. Commonly, a plurality of capacitors are connected in series with each other to jointly strengthen the resistance ability when the potential is rapidly raised, so as to make up for the lack of the ability of the single capacitor to resist the transient voltage. . However, when a plurality of capacitors are connected in series, any single capacitor may also fail, and then cause some degree of current conduction between the single capacitors. Therefore, how to improve the ability of the single capacitors to withstand transient high voltage has become an important issue.

In addition, the impact of transient high voltage or high electric field may cause the ambient temperature in the electronic circuit system to rise sharply. If the capacitor is fortunate enough to withstand transient high voltage damage or dielectric If the capacitor collapses, the capacitor may not be able to withstand the damping effect of high temperature on the capacitor. Therefore, the issues to be solved should further include how to maintain the performance of the capacitor to be gentle or to avoid sharp fluctuations. However, as described in the previous description of capacitor classification by the American Electronics Industry Association, Class I temperature-compensated capacitors and Class II medium- and high-dielectric capacitors have been disclosed to those skilled in the art at the initial structure, development purpose, and scheme design stage. Any Capacitor systems do not have the best of both worlds, so if you want to develop a capacitor product that has both high temperature capacitor performance and resistance to transient voltage damage, it is equivalent to launching a severe product cross-border challenge.

Similar conventional techniques, for example, Japanese Patent Laid-Open No. 2004-107200, which discloses a dielectric ceramic composition formula that can be used in the base metal process. This composition formula will uniformly form M ₄ in the grain boundary phase during the sintering process. R ₆ O (SiO ₄ ) ₆ crystal precipitates (M is selected from at least one element of the alkaline earth group; R is selected from at least one element of the rare earth group), and it is a key factor for improving resistance to voltage breakdown and temperature characteristics. In addition, a few years later, there was another learned technique, such as: Republic of China Patent Publication No. 200846299, which began to further improve the technology disclosed in the aforementioned Japanese Patent Laid-Open No. 2004-107200. First, M ₄ R ₆ O ( The SiO ₄ ) ₆ composite oxide is converted into one of the raw materials of the composition, and then the sintering process is started through the special blending of other sub-components. This can improve the lack of product life and product reliability made by the aforementioned Japanese patent technology based on documentary records. problem. However, when observing the technical solutions of the M ₄ R ₆ O (SiO ₄ ) ₆ composite oxides of the above-mentioned conventional techniques, the only drawback is that the essential properties of this silicon-containing oxide due to the composition of the precipitate are important for the overall temperature and capacitance of the capacitor. The change performance can only reach the EIA-X5R specification level, and there is no way to make further breakthroughs. In other words, the know-how only hints at this severe product cross-border challenge. Finding directions from crystalline precipitates may be a feasible strategy, but those skilled in the art must find other new kinds of crystalline precipitates or new composition formulas in order to be able to be more effective. Further improve capacitor products.

Therefore, how to develop a multilayer ceramic capacitor that does not cause a dielectric breakdown problem when subjected to transient high-voltage or high-energy shocks, is the direction that related manufacturers in this industry are eager to study and improve.

Therefore, in view of the above problems and deficiencies, the inventors have collected relevant information, assessed and considered from various parties, and based on years of experience accumulated in this industry, through continuous trial and error, began to design the resistance of this composite phase structure. Transient high voltage dielectric ceramic body. In addition to having good high voltage resistance, it can also resist dielectric collapse caused by sudden or instantaneous rise in electrical energy or potential. At the same time, it also has temperature capacitance stability in accordance with EIA-X7R capacitor specifications.

The invention is a dielectric ceramic body which is resistant to transient high voltage. Its composition is formed by sintering a plurality of different main components and adding at least one auxiliary component. Among them, the two main components are the first main component BaTiO ₃ , respectively. Two main components ABO ₃ (A is selected from the group of elements consisting of Ba, Sr, Ca; B is selected from the elements Zr or Ti), and the Mohr numbers of the two main components conform to the general formula (100-x ) BaTiO ₃ -xABO ₃ formula ratio (x = 0.1 ~ 30), where x is the mole ratio, and the added at least one secondary component is also called the first secondary component, such as magnesium oxide MgO or manganese carbonate MnCO ₃ . After the dielectric ceramic body was formed by sintering, the dielectric ceramic body was detected by XRD crystal structure diffraction and found to be a composite perovskite structure containing both tetragonal crystal and Orthorhombic crystal. In short, the dielectric ceramic body is sintered to form another composite phase structure with a special diffraction peak under the blending of special main components and sub-components.

In the aforementioned dielectric ceramic body capable of withstanding transient high voltage, the second main component ABO _{3 is} preferably SrZrO ₃ or CaZrO ₃ . When made into multilayer ceramic capacitors and performing different electrical measurements, if two different DC voltage rise rates of 200Vdc / s (measured dielectric strength, referred to as BDV) and 6000Vdc / s (measured dielectric strength) are further observed (Referred to as BDV _H ) test results, it can be found that when there are both tetragonal and rhombohedral crystals in the dielectric ceramic, the insulation group characteristics of the capacitor are significantly improved. The most special BDV _H test results even show that the capacitor has 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 value of dielectric loss gradually decreases, which can effectively prevent the internal energy from being converted into heat energy consumption, so that the temperature inside the capacitor does not occur instantly. The situation increased sharply, which in turn caused the internal electrodes of the base metal to be burned or caused unexpected thermal failure.

In the foregoing dielectric ceramic body capable of withstanding transient high voltage, the Mohr number of the second main component ABO ₃ is controlled in the range of 0.1 to 30 Molar, and the preferred range is 0.1 to 15 Molar. If it exceeds 30 mols, the rhombohedral crystals in the dielectric ceramic will disappear, which will affect the expected technical effect.

In the foregoing dielectric ceramic body capable of withstanding transient high voltage, when the secondary component is the first secondary component, the first secondary component is selected from the group consisting of MgO, ZnO, CuO, GeO, FeO, NiO, MnCO ₃ or CoCO ₃ Either. The metal ions contained in the first sub-component are substituted by Ti ⁴⁺ or Zr ⁴⁺ by acceptor doping, so as to achieve the effect of providing an anti-reduction atmosphere.

In the foregoing dielectric ceramic body capable of withstanding transient high voltage, the secondary component may further include a second secondary component, and the second secondary component is selected from the group consisting of Y ₂ O ₃ , Ho ₂ O ₃ , Ga ₂ O 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 Any of the trivalent ion oxide groups consisting of Yb ₂ O ₃ . The second sub-component can reduce the oxygen vacancies generated during the sintering process in a reducing atmosphere, which improves the insulation resistance value and product reliability. However, when the amount is too large, the dielectric constant may decrease, so it is not suitable to add too much. Furthermore, a third sub-component can be added. The third sub-component is a Si-containing oxide with 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 group. Either. This can reduce the sintering temperature of the dielectric ceramic body and help ion diffusion. At the same time, it can also shorten the powder spacing through the physical action of the high-temperature liquid phase, thereby eliminating the formation of pores. Otherwise, the sintering temperature is too high, in addition to increasing the manufacturing cost, it is even easy to cause damage to the internal electrodes of the capacitor.

In the foregoing dielectric ceramic body capable of withstanding transient high voltages, the Mohr number of any of the secondary components is between 0.1 and 7.0 Molar, and the preferred range is 0.1 to 3.0 Molar. The reason is that when the amount of addition is excessive, it may be unexpected. As a result, the stability of the TCC temperature capacitance curve deviates from the EIA-X7R specification, so special attention should be paid.

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

(1) The capacitor 1 made of the dielectric ceramic body 11 can withstand the high electric energy impact caused by the rapid rise of the potential difference in a short time.

(2) And the ceramic capacitor 1 made of the dielectric ceramic body 11 can avoid the dielectric breakdown phenomenon caused by instant lightning strike or surge, and improve the high voltage resistance performance of the ceramic capacitor 1.

(3) The capacitor 1 prepared by the present invention can have both resistance to transient voltage damage and Compliant with EIA-X7R capacitor specification advantages.

(4) The dielectric ceramic material of the present invention has a good resistance to reduction and sintering, and can be matched with the BME process and has commercial competitiveness.

1‧‧‧ceramic capacitor

11‧‧‧ Dielectric ceramic body layer

12‧‧‧ Internal electrode layer

121, 122‧‧‧ Internal electrode

13‧‧‧External electrode

The first picture is a conventional Class II capacitor chart of the American Electronics Industry Association.

The second figure 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 the embodiment of the present invention.

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

The fifth diagram is an X-Ray diffraction diagram of a preferred embodiment of the present invention.

The sixth figure is the components and test data (1) of the embodiment of the present invention.

The seventh diagram is the composition and test data (2) of the embodiment of the present invention.

In order to achieve the above-mentioned objects and effects, the technical means adopted by the present invention, its structure, and implementation methods are described in detail below with reference to the preferred embodiments of the present invention, whose features and functions are fully understood.

Please refer to the second, third, fourth, fifth, sixth, and seventh figures, which are respectively a side cross-sectional view of the embodiment of the present invention, a preparation flowchart, and a schematic diagram of the capacitance versus DC bias attenuation of the preferred embodiment. -Ray diffraction pattern, constituent components and detection data of the embodiment (1) and constituent components and detection data of the embodiment (2).

It can be clearly seen from FIG. 2 that when the dielectric ceramic body capable of withstanding transient high voltages of the present invention is made into the multilayer ceramic capacitor 1 of the embodiment, the composition of the dielectric ceramic body layer 11 is composed of a plurality of different main components and The secondary components are formed by sintering. Among them, the molar number of the secondary component ranges from 0.1 to 7.0 molar, 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 ABO ₃ according to the embodiment of the present invention refers to SrZrO ₃ or CaZrO ₃ powder, or a powder mixture of SrZrO ₃ and CaZrO ₃ , and the Mohr numbers of the two main components conform to the general formula (100 -x) The formula ratio of BaTiO ₃ -xABO ₃ , x is between 0.1 and 30 moles. When the dielectric ceramic body layer 11 was detected by an XRD diffractometer, it was found that the dielectric ceramic body layer 11 was a composite phase perovskite structure containing both tetragonal and rhombohedral crystals. The diffraction results of the embodiment are shown in Figure 5. . A dielectric ceramic material system sintered according to the X-Ray crystal structure diffraction analysis spectrum (XRD) of the embodiment shown in FIG. 5 according to the formula of (100-x) BaTiO ₃ -xABO ₃ , where x The ratio is Mohr. Compared with the material formula, which is only a single main component, BaTiO ₃ has obvious crystal structure differences. The (100-x) BaTiO ₃ -xABO ₃ dielectric ceramic material system shows a composite phase structure of a tetragonal phase BaTiO ₃ and a rhombohedral phase ABO ₃ (A = Ca, Sr, Ba; B = Zr, Ti). Or alternatively called a two-phase structure.

Further, if the embodiments are prepared as multilayer ceramic capacitors and subjected to electrical measurement, the results can be arranged according to the different components as shown in Figures 6 and 7, where the so-called electrical measurement includes: Capacitive resistance measuring instrument (LCR meter) performs TCC value and loss factor (DF) at a frequency of 1kH and 1Vrms, measures insulation resistance (IR) with a high resistance meter 250Vdc, and uses different voltage rising rates 200Vdc / s (the measured dielectric strength, referred to as BDV) and 6000Vdc / s (the measured dielectric strength, referred to as BDV _H ) are used to measure the ability to withstand transient voltages.

Please refer to the results of FIG. 6 and FIG. 5 at the same time. When a compound perovskite structure with a tetragonal crystal and a rhombohedral crystal exists in the embodiment at the same time, the multilayer ceramic capacitor 1 prepared therefrom has a significant improvement in insulation resistance characteristics Then, comparing the different rising voltage rates of 200Vdc / s and 6000Vdc / s, the BDV _H results of the multilayer ceramic capacitors produced even show the effect of withstanding high transient voltage, that is, the multilayer ceramic capacitors 1 can exert resistance against instantaneous power rise. Damage caused by high voltage or high potential. Specifically, looking at Examples 1 to 11 listed in the sixth figure, when the first sub-component of the dielectric ceramic layer 11 is kept constant, as the Mohr number of the second main component increases, BDV and BDV _H get good values. result. Further, carefully observe Examples 1 to 8 therein, the TCC temperature capacitance value change rate of the prepared multilayer ceramic capacitors in the temperature range of -55 ° C to 125 ° C is maintained within a range of ± 15%, which complies with the EIA-X7R specification. In other words, when the compound perovskite structure of tetragonal crystal and rhombohedral crystal exists in the dielectric ceramic body of the embodiment at the same time, the product characteristics of the multilayer ceramic capacitor prepared therefrom are very superior, and they will have both high transient voltage resistance and EIA compliance. -X7R high temperature capacitor stable characteristics.

Moreover, Examples 1 to 10 also show that when the composite perovskite structure contained in the dielectric ceramic body layer 11 has the effect of suppressing the dielectric loss, and as the second main component SrZrO ₃ or CaZrO ₃ Moore As the number increases, the dielectric loss will decrease. Dielectric loss is a situation of energy conversion, and most of the energy loss is in the form of electrical energy converted to thermal energy. In addition, the dielectric loss is the sum of the losses caused by the phase shift of the electric field (that is, the AC electric field). The amount of this dielectric loss is inversely proportional to the ability to withstand AC voltage. The destruction mechanism of dielectric materials under AC electric field is mostly thermal collapse caused by thermal energy, so the lower the dielectric loss, the better the ability to withstand the AC electric field. For multilayer ceramic appliances 1, the larger the dielectric loss, the easier it is usually to increase the internal temperature of the multilayer ceramic capacitor 1 sharply. If the internal temperature cannot be quickly conducted to the external environment through the external electrode 13 formed of copper or nickel, then The internal electrodes 121, 122 made of base metal may be burned or melted at any time. In addition, the effect of the improved dielectric properties of the composite perovskite structure contained in the dielectric ceramic body layer 11 does not stop there. According to the embodiments 1, 3, 6, 7, 8, 9 listed in the fourth figure , 10 and 11, when the secondary component is maintained, as the Mohr number of the second main component increases, the capacitance value performance of the prepared multilayer ceramic capacitor 1 will improve the resistance to the DC bias. For example, when the DC bias voltage reaches 1.5V / um, the capacitance change rate attenuation of about -20.0% has occurred in Embodiments 1 and 3, but the capacitance change rate attenuation phenomenon of Embodiments 9, 10 and 11 has occurred. However, it is still maintained in the range of -5.0%. In particular, the capacitance change rate of Example 11 is almost unchanged at 0%. If the trends of the curves in the fourth figure are observed, when the dielectric ceramic body layer 11 increases with the second main component, the multilayer ceramic capacitor 1 can be applied to a stronger DC bias environment and has a good resistance to the attenuation of the capacitance value. effect.

Further, in order to describe the technical effects of the present invention in detail, the electrical measurement results will be sequentially analyzed and described according to the embodiments listed in the sixth figure. First, observe the composition formula of each embodiment in the sixth figure. When the second main component is between 0 and 30 mol%, the dielectric strength BDV measured at a lower boost rate of 200 Vdc / s can reach 71 to 119 Vdc / μm. This result is quite good withstand voltage, especially when the content of the second main component is between 3 ~ 11mol%, the dielectric strength BDV is even higher than 100Vdc / μm. It should only be reminded that the chemical composition of Example 1 is only a single main component BaTiO ₃ and a plurality of secondary components are added. The boosting rate condition at 200Vdc / s has 110Vdc / μm, but when the boosting rate is changed to 6000Vdc / s However, the dielectric strength is only 27Vdc / μm. The reason for this is that Example 1 did not add any second main component, so that the XRD diffraction peak showed only a single perovskite crystal structure. Technical effects. If the occurrence of a lightning strike or a surge is considered, the characteristics of Example 1 will cause the dielectric strength value to fluctuate too much, and then it will easily impact the cooperative operation between electronic components in the electronic circuit and cause failure. Therefore, the prepared capacitor is not The stable capacitor expected by the present invention is resistant to instantaneous high-voltage rise. On the other hand, the capacitor expected to resist instantaneous high-voltage rise in the present invention has a dielectric ceramic body layer 11 of which at least 0.1 mole of a second main component is added and a sintered and rhombohedral composite is formed. Perovskite structure. Taking Example 4 and Example 7 as an example, because it contains a second main component in a specific proportion, the sintering will cause the presence of both tetragonal and rhombohedral crystals in the dielectric ceramic body layer. This composite perovskite structure The values of the dielectric strength of BDV and BDV _H tend to be milder, indicating that sudden shocks to high voltages will not cause excessive fluctuations, and the capacitance temperature changes also comply with EIA-X7R specifications under the action of multiple secondary components. Regardless of the momentary high voltage change or high temperature change environment, from the perspective of product reliability, they will all be more stable capacitor products.

Furthermore, according to the results of the examples shown in the sixth figure, when the content of the second main component is between 5 and 15 moles, the measured BDV _{H is} higher than 70Vdc / μm, and this result is not limited to the second main component. 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 main component shown in Examples 12 to 21 is maintained at 5 moles, the ratio of SrZrO ₃ / CaZrO ₃ can be arbitrarily changed from 0 to 1. As a result, it can still obtain very good transient voltage resistance and meet EIA- X7R specification. However, if the CaZrO ₃ mole number added to the second main component is too high, the TCC temperature capacitance stability will start to deteriorate. Taking Example 21 as an example, although it has good BDV _H characteristics, the TCC value measured at a high temperature of 125 ° C. approaches the -15% critical limit required by the EIA-X7R specification.

Please refer to each embodiment in the seventh figure. The seventh figure is based on the Mohr numbers of the first main component and the second main component described in Example 4 and is kept constant. Then, the addition amount of various different sub-components is arbitrarily changed. And proportion, the purpose is to further optimize the TCC temperature-capacitance curve change rate and adjust the insulation resistance under the stable foundation of the composite perovskite structure. Take the first sub-components MgO and MnCO ₃ as examples. Among them, MgO has a good effect on stabilizing the change rate of the TCC temperature-capacitance curve in the range of -55 ~ 125 ° C. The specific results are shown in Examples 22-28. The amount of MgO added gradually increased from 0.5 Moore to 7.0 Moore, and the rate of change in capacitance at 125 ° C converged from -14.5% to -6.6%. At the same time, as the amount of MgO added increased, the insulation resistance also gradually increased from 66.9GΩ to 100.9GΩ. Another first sub-component, MnCO ₃ , is specifically shown in Examples 29 to 33. As the addition amount increases, it also has the effects of improving the stability of the temperature capacitor and the insulation resistance.

Also, observe the examples described in the seventh figure, in which the trivalent metal ion oxides such as the second sub-component Y ₂ O ₃ and Ho ₂ O ₃ are added, because the second sub-component can usually reduce the reducing atmosphere during sintering. The generated oxygen vacancy, so as the amount of addition increases, the insulation resistance also tends to increase, as shown in Example 31 and Examples 34 to 41. When the amount of Y ₂ O _{3 is} 1 mole, the insulation resistance is 68.7 GΩ. As the amount of Y ₂ O _{3 is} increased to 1.5, 2, 3, and 5 moles, the insulation resistance is also increased to 68.6 GΩ, 82.3 GΩ, 124.4 GΩ, and 149.4GΩ. Therefore, the increase in the amount of the second sub-component will greatly improve the insulation resistance characteristics, and the temperature stability of the TCC capacitor will hardly fluctuate too much. However, when the amount is too large, the dielectric constant will be lowered. Pay attention. In addition, from Example 34 and Examples 39 to 41, it can be seen that the effects of substitution of atoms between trivalent ions such as Y ₂ O ₃ and Ho ₂ O ₃ occur.

Further, observe each of the embodiments described in the seventh figure, in which a third sub-component 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 examples, 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 moles, there will not be any significant change in dielectric properties. However, if the added amount is as high as 4 mole, the stability of the TCC temperature-capacitance curve will gradually decrease, but it can still meet the EIA-X7R specification, as shown in Example 45. According to the results of the examples listed in the seventh figure, as a whole, no matter what kind of auxiliary component is added, it should be between 0.1 and 7.0 moles, and preferably 0.1 to 3.0 moles, because when the amount is too much, it may be Accidentally causes the stability of the TCC curve to gradually deviate from the EIA-X7R specification or cause other poor dielectric characteristics, so special attention should be paid.

Please refer to the third figure, which is a method for preparing a molded capacitor of a dielectric ceramic body according to an embodiment of the present invention, which can be performed according to the following steps and procedures, wherein:

(A01) Adding the main component can be two main components, namely the first main component BaTiO ₃ and the second main component ABO ₃ . And at the same time

(A02) Add at least one secondary component, which is a different type of secondary component from the main component.

(A03) slurry preparation, toluene, anhydrous alcohol, plasticizer, Binders and dispersants.

(A04) A doctor blade is used to prepare a green embryo thin band.

(A05) Screen printing internal electrode layer.

(A06) Raw embryo preparation, lamination, pressure equalization, cutting and the like.

(A07) Organic matter was burned off.

(A08) Sintering in a reducing atmosphere.

(A09) Reoxidation heat treatment.

(A10) An external electrode was prepared.

(A11) Electrical measurement.

In the foregoing steps (A01) and (A02), the main component and auxiliary component powders are prepared by firstly synthesizing BaCO ₃ , CaCO ₃ , SrCO ₃ , TiO ₂ , Zr ₂ O ₅ and SiO ₂ by common solid-phase synthesis methods. Sintering at a high temperature between 900 ° C and 1300 ° C turns into 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 powders in accordance with the first The proportions of the sixth and seventh graphs are evenly mixed with respect to the molar number.

In the foregoing step (A03), the components are mixed to prepare a ceramic slurry. The dielectric ceramic powders prepared in relative proportions are added, and toluene, anhydrous alcohol, a plasticizer, a binder, and a dispersant are added and mixed uniformly.

In the foregoing step (A04), a ceramic green sheet with a thickness of 25 μm is prepared by a doctor blade method.

In the aforementioned step (A05), the screen-printed internal electrode layer uses a screen-printing method to print commercial silver (Ag), platinum (Pb), copper (Cu) or nickel (Ni) metal paste with a designed internal electrode pattern on the screen. Ceramic green embryos on thin strips.

In the aforementioned step (A06), the preparation of the green embryo mainly refers to three processes of lamination, equalization and cutting. After the ceramic green embryo thin strips printed with the internal electrode pattern are sequentially stacked, each of them is heated by hot water equalization. The raw embryo thin band is compressed tightly and cut into a multilayer ceramic raw embryo that was originally designed.

In the aforementioned step (A07), burning off the organic matter means that the multilayer ceramic green embryo is held in a pure N ₂ environment at a temperature of 330 ~ 500 ° C (heating rate 2 ° C / min) for 6-20 hours to make each organic substance in the green embryo. Burn out completely.

In the aforementioned step (A08), the reduction atmosphere sintering refers to placing the laminated ceramic green body after the organic matter has been burned out, and placed in a reducing atmosphere composed of 98% N ₂ -2% H ₂ and 35 ° C saturated water vapor at 1000 ~ 1400 ° C. (Heating rate: 3 ° C / min) The sintering procedure was performed and the temperature was maintained for 2 hours.

In the previous step (A09), the reoxidation heat treatment is performed after 2 hours of the previous step, and the temperature is lowered to a temperature range of 900 ° C to 1050 ° C (the cooling rate is 4 ° C / min) and the oxygen pressure is 60ppm to 150ppm or the atmosphere An oxidative heat treatment is performed, and then the temperature is gradually lowered to room temperature to obtain a laminated ceramic green body.

In the foregoing step (A10), the external electrode system is prepared by coating electrode paste pastes such as silver (Ag), copper (Cu), nickel (Ni), or tin (Sn) on the inner electrode ends exposed on both sides of the mature embryo. In a pure N ₂ atmosphere, the temperature was raised to 800 ° C. to 900 ° C. (the cooling rate was 15 ° C./min), and then the furnace was cooled down to room temperature to complete the preparation of the multilayer ceramic capacitor sample.

According to the foregoing process steps, the multilayer ceramic capacitor according to the embodiment of the present invention is prepared, as shown in FIG. 7. The multilayer ceramic capacitor 1 includes a plurality of laminated dielectric ceramic body layers 11 and a plurality of internal electrode layers 12 stacked and spaced along the surface of each dielectric ceramic body layer 11. The plurality of internal electrode layers 12 may include a plurality of internal electrodes 121, 122 are arranged alternately with each other, and are separated from each other by the dielectric ceramic body layer 11. Formed external electrodes 13 are formed on the two outer sides of the multilayer ceramic capacitor 1, and each external electrode 13 is connected to the internal electrodes 121 and 122, respectively. Among them, when electrically conductive to the internal electrodes 121 and 122, the dielectric layer 11 is formed. 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 metal materials such as silver (Ag), platinum (Pb), copper (Cu), or nickel (Ni). Nickel (Ni) or copper (Cu) is selected as the nickel internal electrode. The external electrodes 13 may be external electrodes made of metal materials 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 includes a first main component BaTiO ₃ and a second main component ABO _{3. The} two main components conform to the general formula (100-x ) BaTiO ₃ -xABO ₃ formula ratio, and the second main component ABO ₃ , wherein A is selected from any one of the element group consisting of Ba, Sr, Ca, B is selected from Zr or Ti, and the second main The component ABO _{3 is} preferably SrZrO ₃ or CaZrO ₃ , and further added with at least one secondary component for sintering. The formed dielectric ceramic system contains a complex phase structure in which tetragonal crystals and rhombohedral crystals coexist simultaneously, which can achieve resistance to instantaneous potential. The dielectric breakdown effect caused by power rise, and the performance of the temperature capacitor also meets the capacitor specifications of EIA-X7R. However, the above description is only the preferred embodiment of the present invention, and it does not limit the patent scope of the present invention. Therefore, all simple modifications and equivalent structural changes made by using the description and drawings of the present invention should be the same. It is included in the patent scope of the present invention and is incorporated by Chen Ming.

In summary, the above-mentioned instantaneous high-voltage-resistant ceramic capacitor body of the present invention is practically implemented in order to achieve its efficacy and purpose. Therefore, the present invention is a research and development with excellent practicability. In order to meet the application requirements of the invention patent, I filed an application in accordance with the law, and I hope that the trial committee will grant the case at an early date to protect the inventor's hard research and development and creation. If there is any suspicion in the jury of the Bureau, please follow the instructions of the letter, and the inventor will cooperate with all efforts and be honest.

Claims (18)

A dielectric ceramic body capable of withstanding transient high voltages, comprising a first main component BaTiO ₃ and a second main component ABO ₃ , characterized in that the two main components conform to the general formula (100-x) BaTiO ₃ -xABO ₃ Formula ratio (30 ≧ x ≧ 0.1, x is the mole ratio; A is selected from any of the element group consisting of Ba, Sr, Ca; B is selected from the elements Zr or Ti), and further contains at least one side The composition of the dielectric ceramic body is defined by X-ray diffraction analysis, which is a composite structure containing tetragonal perovskite and rhombohedral perovskite, and the content of the second main component is between 1.0 and 15.0 moles. As described in item 1 of the scope of the patent application, a dielectric ceramic body capable of withstanding transient high voltages, wherein the second main component is SrZrO ₃ or CaZrO ₃ . As described in item 1 of the scope of the patent application, a dielectric ceramic body capable of withstanding transient high voltages, wherein the secondary component is the first secondary component, and the content of the secondary component is between 0.1 and 7.0 moles. As described in item 3 of the scope of patent application, a dielectric ceramic body capable of withstanding transient high voltage, wherein the auxiliary component is selected from the group consisting of MgO, ZnO, CuO, GeO, FeO, and NiO. The dielectric ceramic body capable of withstanding transient high voltage as described in item 3 of the scope of patent application, wherein the secondary component is MnCO ₃ or CoCO ₃ . As described in item 3 of the scope of the patent application, the dielectric ceramic body capable of withstanding transient high voltage further includes a second sub-component, and the second sub-component is selected from the group consisting of Y ₂ O ₃ , Ho ₂ O ₃ , and Ga ₂ O. 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 , a group consisting of Tm ₂ O ₃ and Yb ₂ O ₃ . As described in item 6 of the scope of the patent application, the dielectric ceramic body capable of withstanding transient high voltage further includes a third subcomponent, and the third subcomponent is selected from BaSiO ₃ , CaSiO ₃ and (Ba _0.6 Ca _0.4 ) SiO Group of ₃ . As described in item 3 of the scope of patent application, the dielectric ceramic body capable of withstanding transient high voltage further includes a second sub-component, and the second sub-component is selected from BaSiO ₃ , CaSiO ₃ and (Ba _0.6 Ca _0.4 ) SiO Group of ₃ . The dielectric ceramic body capable of withstanding transient high voltage as described in any one of items 2 to 8 of the scope of patent application, wherein the content of any one of the secondary components is between 0.1 and 5.0 mol. A dielectric ceramic body capable of withstanding transient high voltages, comprising a first main component BaTiO ₃ and a second main component ABO ₃ , characterized in that the two main components conform to the general formula (100-x) BaTiO ₃ -xABO ₃ Formula ratio (30 ≧ x ≧ 0.1, x is the mole ratio; A is selected from any of the element group consisting of Ba, Sr, Ca; B is selected from the elements Zr or Ti), and further contains at least one secondary component Among them, the dielectric ceramic body is defined by X-ray diffraction analysis as a composite structure containing a tetragonal perovskite and a rhombohedral perovskite, and the content of the auxiliary component is between 0.1 and 7.0 mol. As described in item 10 of the scope of the patent application, a dielectric ceramic body capable of withstanding transient high voltage, wherein the second main component is SrZrO ₃ or CaZrO ₃ . The dielectric ceramic body capable of withstanding transient high voltage as described in item 10 of the patent application scope, wherein the subsidiary component is a compound containing a metal element. According to the instantaneous high-voltage-resistant dielectric ceramic body described in item 12 of the scope of the patent application, the auxiliary component is selected from the group consisting of MgO, ZnO, CuO, GeO, FeO, and NiO. The dielectric ceramic body capable of withstanding transient high voltage as described in item 12 of the scope of the patent application, wherein the secondary component is MnCO ₃ or CoCO ₃ . The dielectric ceramic body capable of withstanding transient high voltage as described in item 12 of the patent application scope, further comprising a second sub-component, and the second sub-component is selected from the group consisting of Y ₂ O ₃ , Ho ₂ O ₃ , and Ga ₂ O. 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 , a group consisting of Tm ₂ O ₃ and Yb ₂ O ₃ . As described in item 15 of the scope of the patent application, the dielectric ceramic body capable of withstanding transient high voltage further includes a third sub-component, and the third sub-component is selected from BaSiO ₃ , CaSiO ₃ and (Ba _0.6 Ca _0.4 ) SiO Group of ₃ . The dielectric ceramic body capable of withstanding transient high voltage as described in item 12 of the patent application scope, further comprising a second sub-component, and the second sub-component is selected from BaSiO ₃ , CaSiO ₃ and (Ba _0.6 Ca _0.4 ) SiO Group of ₃ . According to any one of claims 11 to 17, the dielectric ceramic body capable of withstanding transient high voltages, wherein the content of any of these secondary components is between 0.1 and 5.0 mol.