TWI551442B - Layered ceramic electronic components and pressureless sintering method co - Google Patents

Description

Laminated electronic ceramic component and its pressureless co-sintering method

The invention relates to a method for non-compressive co-sintering of high permittivity dielectrics and low permittivity dielectrics under a reducing atmosphere, in particular to obtain an ideal co-firing. A laminated electronic ceramic component that matches and reacts and reduces electrostrictivity of the element and its pressureless co-sintering process.

Because different material systems have different essential characteristics, how to integrate individual advantages into component characteristics and combine different material systems through Co-firing is an important key technology.

For example, in the Republic of China Patent No. 563271, the magnetic material (iron oxide) and the non-magnetic material (glass) are co-fired, and the electrical requirements of different parts of the common mode filter are provided by the electrical properties of different materials, thereby improving the different filter types. Electrical characteristics.

In U.S. Patent 4,746,557, the inductor formed by the magnetic green sheet and the capacitance formed by the Dielectric Green Sheet are simultaneously designed in one element at 800 ° C to 1000 ° C. The material with inductance and capacitance characteristics is co-sintered at a temperature to integrate an element having both Inductor and Capacitor characteristics.

In the Republic of China Patent No. I367504, a highly integrated wafer varistor is described. The resistor is mainly made of a functional sheet on an insulating ceramic substrate, wherein the functional sheet mentioned comprises a dielectric ceramic material. The piezoelectric ceramic material, the magnetic ceramic material semiconductor material, etc. are polished by the insulating ceramic substrate to form a plurality of grooves to improve the joint strength at the interface and improve the co-firing effect of the heterogeneous ceramic.

In addition to the aforementioned co-fired patented technology between ceramic materials of different compositions and characteristics, there are also many patents emphasizing low-temperature co-firing characteristics (co-firing temperature <950 ° C), for example, in U.S. Patent 5,144,526, A ceramic component-based structural design, in which a high dielectric ceramic material is inserted into the component structure for capacitor element realization by low temperature co-firing (LTCC). The Republic of China Patent No. 428300 is a passive component fabricated by coating a high dielectric ceramic material with a different dielectric type of a low dielectric ceramic material.

DuPont also uses the concept of different high- and low-dielectric ceramic materials for co-firing, and proposes a series of patents. In its US patent 6827800 and the Republic of China patent I226319, the internal tape is added to the primary tape. (Constraining Layer), at the same time adding a release layer (Release Layer) at one end of the surface layer has produced a structure that can suppress the shrinkage of the x and y directions, wherein the main band has a dielectric constant between 6 and 10, while the internal The dielectric constant of the confinement band is between 10 and 5000.

In addition, in U.S. Patent No. 7,068,492, 70, 670, 626 and the Republic of China Patent Nos. I277512, I308106, and I280955, the dielectric constant of a high dielectric material is greater than 8 or higher, and the low dielectric material is less than 8 or less. The electrical constant is corrected to between 7 and 9, and illustrates the use of three or more different dielectric materials to achieve a flat, distortion-free, zero-shrink ceramic component or composite or module or package. The company is in US patent 20060162844 and the Republic of China patent In I278879, the characteristics of the dielectric material used are further corrected, and a high dielectric constant band structure is inserted into the main band of the above design and the internal confinement band to perform co-firing of the capacitor, wherein the high dielectric constant band is used. The dielectric constant is at least 20, and the k values of the high and low dielectric materials used are all below 250. The above DuPont patents are all carried out by low temperature co-firing, that is, the sintering temperature is lower than 950 °C. In U.S. Patent No. 7,141,129, a co-firing technique is adopted in which the k-value range of the dielectric material is greater than 2000, and the K-value of the low-dielectric material is still less than 20, but the patent is still in the technical field of low-temperature co-firing.

However, considering the manufacturing technology and material cost of today's laminated electronic ceramic components (such as laminated ceramic capacitors), the high temperature (>1100 ° C) reducing atmosphere sintering process is still the mainstream. Therefore, how to introduce the above-mentioned co-firing concept into the current sintering process, so that the fabricated components have more meta-characteristics, is the subject to be solved in the art.

In order to solve the above problems of the prior art, an object of the present invention is to provide a non-constrained sintering treatment method for a high dielectric constant ceramic material and a low dielectric constant ceramic material under a reducing atmosphere. In order to obtain an ideal co-firing matching and reactive laminated electronic ceramic component and its pressureless co-sintering method.

In order to solve the above problems of the prior art, another object of the present invention is to provide a high-capacitance dielectric property capable of maintaining a high dielectric constant ceramic material, and to utilize low-voltage electricity and low dissipation of a low dielectric constant ceramic material. A laminated electronic ceramic component having the advantages of coefficient characteristics and reducing electrostrictivity of the element and its pressureless co-sintering method.

In order to solve the above problems of the prior art, another object of the present invention is to provide a laminated electronic ceramic component having low dielectric loss, high insulation resistance, high dielectric breakdown voltage and temperature stability, and a pressureless co-sintering method thereof. .

In order to achieve the above object, the laminated electronic ceramic component of the present invention and the pressureless co-sintering method thereof are controlled by the selection of the material composition structure and the co-firing process parameter, so that the high/low dielectric constant ceramic material can be under a reducing atmosphere (oxygen Partial pressure: 10 ^-12 ~ 10 ^-20 atm) is produced by pressureless co-firing, and the working temperature is greater than or equal to 1150 °C.

Among them, the high dielectric constant ceramic material has a k value of > 1500; and the low dielectric constant ceramic material has a K value of <100. At the same time, through the staggered laminate design, a high dielectric constant ceramic material or a low dielectric constant ceramic material is used as a reaction layer or a cap layer structure of the laminated electronic ceramic component to form a ceramic material having both a high dielectric constant and a low dielectric constant ceramic. A laminated electronic ceramic component of the material, the internal electrode of which is made of nickel metal.

The laminated electronic ceramic component of the invention and the pressureless co-sintering method thereof provide a dielectric ceramic composition and a preparation method capable of high-temperature pressureless co-firing in a reducing atmosphere, which are mutually crystallized by using a perovskite structure. The lattice structure is similar, and the interaction is better under high temperature, forming a reaction structure and improving the binding of the heterogeneous interface between the co-firing of different material compositions.

Among them, the high dielectric constant ceramic material is mainly composed of a BaTiO ₃ -based ferroelectric material, and the molar ratio of Ba/Ti is between 0.99 and 1.06, and the particle size is small. (D ₅₀ ) ranges from 0.1 to 0.5 μm and various oxide additives are added so that the material composition can be sintered under a reducing atmosphere, and the material has a dielectric constant of more than 1000 after sintering.

The oxide additive composition is based on 100% by weight of the main phase barium titanate, which comprises: 0.32 to 2.70 wt% barium carbonate (BaCO ₃ ), 0 to 0.06 wt% molybdenum trioxide (MoO ₃ ), 0.20~ 0.55wt% cerium oxide (SiO ₂ ), 0.17~0.72wt% yttrium oxide (Y ₂ O ₃ ), 0.04~0.34wt% magnesium oxide (MgO), 0~0.07wt% bismuth pentoxide (Nb ₂ O ₅ ), 0.11~0.28wt% manganese carbonate (MnCO ₃ ), 0~1.61wt% yttrium oxide (Yb ₂ O ₃ ), 0~0.51wt% alumina (Al ₂ O ₃ ), 0~0.50wt% calcium carbonate ( CaCO ₃ ), 0~0.21wt% zirconium dioxide (ZrO ₂ ), 0~0.05wt% antimony trioxide (Sm ₂ O ₃ ), 0~0.28wt% yttrium oxide (Dy ₂ O ₃ ), 0~0.10 Wt% titanium dioxide (TiO ₂ ), 0-0.04 wt% vanadium pentoxide (V ₂ O ₅ ), 0-0.13 wt% strontium carbonate (SrCO ₃ ), and 0-0.23 wt% tin oxide (SnO). The above oxide additive configuration can be used to control the particle size of the main phase powder, control the dielectric properties and the desired co-sintering temperature and atmosphere environment.

Preferably, the composition of the above oxide additive comprises: 0.32 to 2.70 wt% of barium carbonate (BaCO ₃ ), 0.001 to 0.06 wt% of molybdenum trioxide (MoO ₃ ), and 0.20 to 0.55 wt% of cerium oxide (SiO ₂ ). , 0.17~0.72wt% yttrium oxide (Y ₂ O ₃ ), 0.04~0.34wt% magnesium oxide (MgO), 0.001~0.07wt% bismuth pentoxide (Nb ₂ O ₅ ), 0.11~0.28wt% manganese carbonate ( MnCO ₃ ), 0.001 to 1.61% by weight of yttrium oxide (Yb ₂ O ₃ ), 0.001 to 0.51% by weight of aluminum oxide (Al ₂ O ₃ ), 0.001 to 0.50% by weight of calcium carbonate (CaCO ₃ ), 0.001 to 0.21% by weight Zirconium oxide (ZrO ₂ ), 0.001 to 0.05 wt% of antimony trioxide (Sm ₂ O ₃ ), 0.001 to 0.28 wt% of yttrium oxide (Dy ₂ O ₃ ), 0.001 to 0.10 wt% of titanium oxide (TiO ₂ ), 0.001~ 0.04 wt% vanadium pentoxide (V ₂ O ₅ ), 0.001 to 0.13 wt% strontium carbonate (SrCO ₃ ), and 0.001 to 0.23 wt% tin oxide (SnO).

Among them, low dielectric constant ceramic materials are mainly dielectric ceramic materials with dielectric constant below 100, but have excellent low dielectric loss (Low Dissipation Factor, DF<0.1%) and stable temperature dielectric. Characteristics (Temperature-Capacitance Coefficient, △C/C≦1000ppm in -55 ° C ~ 125 ° C), in order to make this material has a sintering characteristics in a reductive atmosphere, and add appropriate additives.

The low dielectric constant ceramic material has a particle size (D ₅₀ ) ranging from 0.3 to 0.6 μm, and includes: 21.42 to 35.85 wt% calcium carbonate (CaCO ₃ ), and 0 to 21.31 wt% strontium carbonate (SrCO _{3 ).} ), 0~7.97wt% barium carbonate (BaCO ₃ ), 0~11.20wt% magnesium oxide (MgO), 1.36~14.86wt% titanium dioxide (TiO ₂ ), 6.74~51.30wt% zirconium dioxide (ZrO ₂ ), 0 ~5.83wt% zinc oxide (ZnO), 0~1.30wt% manganese carbonate (MnCO ₃ ), 0.59~26.58wt% cerium oxide (SiO ₂ ), 0.16~1.53wt% cerium oxide (HfO ₂ ), 0~ 0.11 wt% of tantalum pentoxide (Ta ₂ O ₅ ), 0 to 0.12 wt% of yttrium oxide (Y ₂ O ₃ ), and 0 to 0.18 wt% of alumina (Al ₂ O ₃ ). The dielectric composition, the sintering temperature and the suitable sintering atmosphere environmental conditions can be adjusted by the composition change of the above materials and the particle size of the powder.

Preferred are the low dielectric constant ceramic material, comprising: 21.42 ~ 35.85wt% calcium carbonate _{(CaCO 3), 0.001 ~ 21.31wt} % strontium carbonate _{(SrCO 3), 0.001 ~ 7.97wt} % barium carbonate (BaCO ₃₎ 0.001~11.20wt% magnesium oxide (MgO), 1.36~14.86wt% titanium dioxide (TiO ₂ ), 6.74~51.30wt% zirconium dioxide (ZrO ₂ ), 0.001~5.83wt% zinc oxide (ZnO), 0.001~1.30 Wt% manganese carbonate (MnCO ₃ ), 0.59~26.58wt% cerium oxide (SiO ₂ ), 0.16~1.53wt% cerium oxide (HfO ₂ ), 0.001~0.11wt% bismuth pentoxide (Ta ₂ O ₅ ) 0.001 to 0.12 wt% of yttrium oxide (Y ₂ O ₃ ) and 0.001 to 0.18 wt% of alumina (Al ₂ O ₃ ).

Then, based on the high dielectric constant ceramic material and the low dielectric constant ceramic material, nickel metal or its alloy is used as an electrode to form a high dielectric constant ceramic layer and a high dielectric constant electrode layer (ie, coated metal). a high dielectric constant ceramic layer of the electrode), a low dielectric constant ceramic layer and a low dielectric constant electrode layer (ie, a metal dielectric low dielectric constant ceramic layer).

Next, the internal reaction layer of the element is composed of a high dielectric constant ceramic structure layer and a low dielectric constant ceramic structure layer, and the staggered laminate design of the two structural layers may be symmetric or asymmetric. In the reaction layer, at least one of a high dielectric constant ceramic structural layer and a low dielectric constant ceramic structural layer exists.

The high dielectric constant ceramic layer and the high dielectric constant electrode layer are composed of a high dielectric constant ceramic structural layer, and the low dielectric constant ceramic layer and the low dielectric constant electrode layer are composed of a low dielectric constant ceramic structure. Floor.

Among them, the high dielectric constant ceramic structure layer is designed by a staggered laminate of high dielectric constant electrode layers to achieve capacitance characteristics. And the size of the staggered area between the electrodes is used, and the thickness of the high dielectric constant ceramic layer between the electrodes is controlled, thereby achieving the purpose of regulating the capacitance value. The electrode pattern can be continuous, discontinuous or floating. The high dielectric constant ceramic structural layer may also be entirely a ceramic layer. The high dielectric constant ceramic substrate of the high dielectric constant ceramic layer and the high dielectric constant electrode layer may be the same or similar composition components treated under a single sintering condition.

Among them, the low dielectric constant ceramic structure layer is designed by a staggered laminate of low dielectric constant electrode layers to achieve capacitance characteristics. And the use of the cross-sectional area between the electrodes, and the thickness of the low dielectric constant ceramic layer between the control electrodes, thereby achieving the purpose of regulating the capacitance value. Wherein, the electrode pattern form may be continuous or discontinuous or floating. The low dielectric constant ceramic structural layer may also be entirely a ceramic layer. The low dielectric constant ceramic substrate of the low dielectric constant ceramic layer and the low dielectric constant electrode layer may be the same or similar composition components treated under a single sintering condition.

The high dielectric constant ceramic layer, the high dielectric constant electrode layer, the low dielectric constant ceramic layer and the low dielectric constant electrode layer may be the same or different thickness dimensions.

Wherein, the electrode thickness in the high dielectric constant ceramic structure layer and the electrode thickness of the electrode layer in the low dielectric constant ceramic structure layer may also be the same or different thickness sizes, and the thickness of each electrode layer needs to be less than or equal to the corresponding High dielectric constant ceramic structural layer and low dielectric constant ceramic structural layer thickness.

The cover layer structure is at least one of a low dielectric constant ceramic layer or a high dielectric constant ceramic layer, and the thickness and composition of the upper and lower cover layers may be the same or different, and the thickness of the cover layer is at least greater than 30 μm. And the ceramic material composition of the cover layer and the ceramic material of the reaction layer may be the same or different.

Further, the bonding regions between the respective structural layers may be sintered through the same or different ceramic layers, or the ceramic layers and the electrode layers may be joined to each other to form a co-firing reaction bonding interface.

Further, the present invention is produced by pressureless co-sintering in the following manner, and further, two or more kinds of material systems are co-fired in a reducing atmosphere, and are realized in element fabrication. The co-sintering process is as follows: First, the capacitor element body according to the above-mentioned completed laminated structure is subjected to a pre-burning process at a temperature T1; thereafter, the pre-burned capacitor element body is subjected to a temperature T2 higher than the temperature T1. In the burn-off process, the above atmosphere is controlled at an oxygen partial pressure of 10 ^-6 to 10 ^-12 atm; then, the temperature is continuously raised to T3, and a mixture of moisture, hydrogen or nitrogen is introduced to control the reducing atmosphere (10 ^-12). Sintering process between heterogeneous materials at ~10 ^-20 atm partial pressure; finally, the sintering temperature is lowered to temperature T4, and a mixture of moisture, nitrogen and oxygen is introduced to control the oxygen partial pressure. 10 ^-7 ~ 10 ^-15 atm for re-oxidation process, where T3>T4>T2 T1, and the high temperature co-firing curve can be carried out under a reducing atmosphere. Wherein, the temperatures T1 and T2 of the pre-burning and burning process mentioned above are carried out at a temperature of 200 ° C to 900 ° C, and the pre-burning and burning processes may be carried out separately or in combination; the temperature T3 range of the sintering process is The temperature is between 1150 ° C and 1350 ° C; while the temperature T4 of the reoxidation process falls between 950 ° C and 1150 ° C. At the same time, the rise and fall rates of each process should be controlled within the range of 1.5 °C / min ~ 15 ° C / min.

S01~S02‧‧‧Step process

S021~S024‧‧‧Step procedure

100‧‧‧ first cover

200‧‧‧second cover

300‧‧‧Reaction layer

400‧‧‧ Nickel metal electrode layer

500‧‧‧High dielectric constant ceramic structure

501‧‧‧High dielectric constant ceramic layer

502‧‧‧High dielectric constant electrode layer

600‧‧‧Low dielectric constant ceramic structural layer

601‧‧‧Low dielectric constant ceramic layer

602‧‧‧Low dielectric constant electrode layer

1A is a flow chart of a pressureless co-sintering method for a high dielectric constant ceramic structural layer of the present invention; FIG. 1B is a detailed flow chart of step S02; FIG. 2 is a schematic view of a high dielectric constant ceramic structural layer of the present invention; 3 is a schematic view of a low dielectric constant ceramic structural layer of the present invention; FIG. 4 is a schematic view of a laminated electronic ceramic component of the present invention; FIG. 5A is a schematic diagram of continuous printing of a nickel metal electrode layer; FIG. 5B is a nickel metal electrode layer. A schematic diagram of continuous printing; and Figure 5C is a schematic diagram of floating printing of a nickel metal electrode layer.

The specific embodiments are described below to illustrate the embodiments of the invention, but are not intended to limit the scope of the invention.

1A-1B, the pressureless temperature co-sintering method of the laminated electronic ceramic component of the present invention comprises the following steps: S01: a high dielectric constant ceramic junction layer with a k value (dielectric constant) greater than 1500 and a k value of less than 100. The low dielectric constant ceramic structure layer is alternately laminated to form a laminated electronic ceramic component; S02: the laminated electronic ceramic component is subjected to pressureless sintering at a temperature of 1150 ° C to 1350 ° C in a reducing atmosphere of 10 ^-6 ~ 10 ^-20 atm.

Wherein, the laminated electronic ceramic component is sintered in a reducing atmosphere at a temperature of 10 ^-6 to 10 ^-20 atm, wherein the process comprises: S021: pre-burning the laminated electronic ceramic component at 200 ° C to 900 ° C; S022: pre-burning The removed laminated electronic ceramic component is fired in a reducing atmosphere of 10 ^-6 ~ 10 ^-12 atm and higher than the pre-burning temperature; S023: the temperature is raised to 1150 ° C ~ 1350 ° C, and moisture is introduced at the same time. Nitrogen and hydrogen mixed gas, and sintered in a heterogeneous material in a reducing atmosphere of 10 ^-12 ~ 10 ^-20 atm; S024: The temperature is lowered to 950 ° C ~ 1150 ° C, and the moisture, nitrogen and The hydrogen mixed gas is subjected to a reoxidation process in a reducing atmosphere of 10 ^-7 to 10 ^-15 atm.

The high dielectric constant ceramic structural layer described above is made of a high dielectric constant ceramic material. The following is an example of a composition of a high dielectric constant ceramic material and a method for fabricating a high dielectric constant ceramic structural layer:

Example 1-1: The composition of the high dielectric constant ceramic material included a main phase material and an oxide additive, and a dielectric constant (hereinafter referred to as k value) was 4500. The main phase material is BaTiO ₃ , the molar ratio of Ba/Ti is 0.99, the particle size (D ₅₀ ) is 0.5 μm, and the oxide additive composition is based on 100% by weight of the main phase BaTiO ₃ . Including: BaCO ₃ (cerium carbonate): 1.22% by weight, MoO ₃ (molybdenum trioxide): 0.05% by weight, SiO ₂ (cerium oxide): 0.46% by weight, Y ₂ O ₃ (cerium oxide): 0.34% by weight, MgO (magnesium oxide): 0.2% by weight, Nb ₂ O ₅ (antimony pentoxide): 0.05% by weight, MnCO ₃ (manganese carbonate): 0.13% by weight, Al ₂ O ₃ (alumina): 0.22% by weight, ZrO ₂ (zirconium dioxide): 0.04% by weight.

The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (The phthalates or phosphates) are sufficiently stirred to form a ceramic slurry, and a high dielectric constant ceramic layer having a thickness of 2 to 5 μm is formed by coating, and then printed on a high dielectric constant ceramic layer. A nickel metal electrode to form a high dielectric constant ceramic electrode layer.

Example 1-2: High dielectric constant The composition of the ceramic material consisted of a main phase material and an oxide additive having a k value of 2,200. The main phase material is BaTiO ₃ , the molar ratio of Ba/Ti is 1.03, the particle size (D ₅₀ ) is 0.3 μm, and the oxide additive composition is based on 100% by weight of the main phase BaTiO ₃ . Including: BaCO ₃ (cerium carbonate): 2.27 wt%, MoO ₃ (molybdenum trioxide): 0.05 wt%, SiO ₂ (ceria): 0.55 wt%, Y ₂ O ₃ (yttria): 0.3 wt%, MgO (magnesium oxide): 0.2% by weight, Nb ₂ O ₅ (antimony pentoxide): 0.07% by weight, MnCO ₃ (manganese carbonate): 0.11% by weight, Yb ₂ O ₃ (cerium oxide): 0.49% by weight, Sm ₂ O ₃ (antimony trioxide): 0.03 wt%, Dy ₂ O ₃ (yttria): 0.18 wt%.

The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (The phthalates or phosphates) are sufficiently stirred to form a ceramic slurry, and a high dielectric constant ceramic layer having a thickness of 2 to 5 μm is formed by coating, and then printed on a high dielectric constant ceramic layer. A nickel metal electrode to form a high dielectric constant ceramic electrode layer.

Example 1-3: The composition of the high dielectric constant ceramic material includes a main phase material and an oxide additive having a k value of 4,000. The main phase material is BaTiO ₃ , the molar ratio of Ba/Ti is 1.03, the particle size (D ₅₀ ) is 0.4 μm, and the oxide additive composition is based on 100% by weight of the main phase BaTiO ₃ . Including: BaCO ₃ (cerium carbonate): 0.99 wt%, MoO ₃ (molybdenum trioxide): 0.06 wt%, SiO ₂ (cerium oxide): 0.49 wt%, Y ₂ O ₃ (cerium oxide): 0.67 wt%, MgO (magnesium oxide): 0.2% by weight, Nb ₂ O ₅ (niobium pentoxide): 0.06 wt%, MnCO ₃ (manganese carbonate): 0.13 wt%, Yb ₂ O ₃ (ruthenium oxide): 0 to 0.33 wt% Al ₂ O ₃ (alumina): 0.42% by weight, ZrO ₂ (zirconium dioxide): 0.15% by weight, Dy ₂ O ₃ (cerium oxide): 0.12% by weight, and TiO ₂ (titanium dioxide): 0.1% by weight.

The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (The phthalates or phosphates) are sufficiently stirred to form a ceramic slurry, and a high dielectric constant ceramic layer having a thickness of 2 to 5 μm is formed by coating, and then printed on a high dielectric constant ceramic layer. A nickel metal electrode to form a high dielectric constant ceramic electrode layer.

Examples 1-4: High dielectric constant ceramic materials consisting of a main phase material and an oxide additive having a k value of 3,300. The main phase material is BaTiO ₃ , the molar ratio of Ba/Ti is 1.05, the particle size (D ₅₀ ) is 0.35 μm, and the oxide additive composition is based on 100% by weight of the main phase BaTiO ₃ . Including: BaCO ₃ (cerium carbonate): 0.82% by weight, MoO ₃ (molybdenum trioxide): 0.03% by weight, SiO ₂ (cerium oxide): 0.22% by weight, Y ₂ O ₃ (cerium oxide): 0.17% by weight, MgO (magnesium oxide): 0.04% by weight, MnCO ₃ (manganese carbonate): 0.28% by weight, Yb ₂ O ₃ (cerium oxide): 0.82% by weight, and Al ₂ O ₃ (alumina): 0.17% by weight.

The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (phthalate or phosphate) is fully stirred to form a ceramic slurry, which is coated and formed. A high dielectric constant ceramic layer having a thickness of 2 to 5 μm is formed, and then a nickel metal electrode is printed on the high dielectric constant ceramic layer to form a high dielectric constant ceramic electrode layer.

Examples 1-5: The composition of the high dielectric constant ceramic material includes a main phase material and an oxide additive having a k value of 2,500. The main phase material is BaTiO ₃ , the molar ratio of Ba/Ti is 0.99, the particle size (D ₅₀ ) is 0.25 μm, and the oxide additive composition is based on 100% by weight of the main phase BaTiO ₃ . Including: BaCO ₃ (cerium carbonate): 1.81% by weight, MoO ₃ (molybdenum trioxide): 0.04% by weight, SiO ₂ (cerium oxide): 0.43% by weight, Y ₂ O ₃ (cerium oxide): 0.44% by weight, MgO (magnesium oxide): 0.08 wt%, Nb ₂ O ₅ (niobium pentoxide): 0.06 wt%, MnCO ₃ (manganese carbonate): 0.27 wt%, Yb ₂ O ₃ (ruthenium oxide): 1.6 wt%, Al ₂ O ₃ (alumina): 0.22% by weight, CaCO ₃ (calcium carbonate): 0.12% by weight, ZrO ₂ (zirconium dioxide): 0.15% by weight.

The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (The phthalates or phosphates) are sufficiently stirred to form a ceramic slurry, and a high dielectric constant ceramic layer having a thickness of 2 to 5 μm is formed by coating, and then printed on a high dielectric constant ceramic layer. A nickel metal electrode to form a high dielectric constant ceramic electrode layer.

Examples 1-6: The composition of the high dielectric constant ceramic material includes a main phase material and an oxide additive having a k value of 2,000. The main phase material is BaTiO ₃ , the molar ratio of Ba/Ti is 1.03, the particle size (D ₅₀ ) is 0.15 μm, and the oxide additive composition is based on 100% by weight of the main phase BaTiO ₃ . Including: BaCO ₃ (cerium carbonate): 1.19 wt%, MoO ₃ (molybdenum trioxide): 0.06 wt%, SiO ₂ (ceria): 0.48 wt%, Y ₂ O ₃ (yttria): 0.44 wt%, MgO (magnesium oxide): 0.2% by weight, Nb ₂ O ₅ (antimony pentoxide): 0.06% by weight, MnCO ₃ (manganese carbonate): 0.13% by weight, Yb ₂ O ₃ (cerium oxide): 1.03% by weight, Al ₂ O ₃ (alumina): 0.51% by weight, CaCO ₃ (calcium carbonate): 0.5% by weight.

The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (The phthalates or phosphates) are sufficiently stirred to form a ceramic slurry, and a high dielectric constant ceramic layer having a thickness of 2 to 5 μm is formed by coating, and then printed on a high dielectric constant ceramic layer. A nickel metal electrode to form a high dielectric constant ceramic electrode layer.

Example 1-7: The composition of the high dielectric constant ceramic material consisted of a main phase material and an oxide additive having a k value of 3,500. The main phase material is BaTiO ₃ , the molar ratio of Ba/Ti is 1.06, the particle size (D ₅₀ ) is 0.35 μm, and the oxide additive composition is based on 100% by weight of the main phase BaTiO ₃ . Including: BaCO ₃ (cerium carbonate): 1.06 wt%, MoO ₃ (molybdenum trioxide): 0.03 wt%, SiO ₂ (cerium oxide): 0.25% by weight, Y ₂ O ₃ (cerium oxide): 0.72% by weight, MgO (magnesium oxide): 0.34% by weight, Nb ₂ O ₅ (niobium pentoxide): 0.05% by weight, MnCO ₃ (manganese carbonate): 0.19% by weight, Al ₂ O ₃ (alumina): 0.2% by weight, ZrO ₂ (zirconia): 0.21% by weight, V ₂ O ₅ (vanadium pentoxide): 0.04% by weight, SrCO ₃ (cerium carbonate): 0.12% by weight.

The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (The phthalate or phosphate) is sufficiently stirred to form a ceramic slurry, and then a nickel metal electrode is printed on the high dielectric constant ceramic layer to form a high dielectric constant ceramic electrode layer.

Example 1-8: The composition of the high dielectric constant ceramic material consisted of a main phase material and an oxide additive having a k value of 2,400. The main phase material is BaTiO ₃ , the molar ratio of Ba/Ti is 1.06, the particle size (D ₅₀ ) is 0.25 μm, and the oxide additive composition is based on 100% by weight of the main phase BaTiO ₃ . Including: BaCO ₃ (cerium carbonate): 0.32% by weight, SiO ₂ (cerium oxide): 0.2% by weight, Y ₂ O ₃ (cerium oxide): 0.23% by weight, MgO (magnesium oxide): 0.13% by weight, Nb ₂ O ₅ (antimony pentoxide): 0.02% by weight, MnCO ₃ (manganese carbonate): 0.19% by weight, Yb ₂ O ₃ (cerium oxide): 1.31% by weight, Al ₂ O ₃ (alumina): 0.21% by weight, SnO (tin oxide): 0.23 wt%.

The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (The phthalates or phosphates) are sufficiently stirred to form a ceramic slurry, and a high dielectric constant ceramic layer having a thickness of 2 to 5 μm is formed by coating, and then printed on a high dielectric constant ceramic layer. A nickel metal electrode to form a high dielectric constant ceramic electrode layer.

Examples 1-9: High dielectric constant ceramic materials consisting of a main phase material and an oxide additive having a k value of 3,400. The main phase material is BaTiO ₃ , the molar ratio of Ba/Ti is 1.06, the particle size (D ₅₀ ) is 0.35 μm, and the oxide additive composition is based on 100% by weight of the main phase BaTiO ₃ . Including: BaCO ₃ (cerium carbonate): 0.74% by weight, MoO ₃ (molybdenum trioxide): 0.02% by weight, SiO ₂ (cerium oxide): 0.25% by weight, Y ₂ O ₃ (cerium oxide): 0.23% by weight, MgO (magnesium oxide): 0.1% by weight, Nb ₂ O ₅ (antimony pentoxide): 0.03% by weight, MnCO ₃ (manganese carbonate): 0.25% by weight, Yb ₂ O ₃ (cerium oxide): 0.17% by weight, Al ₂ O ₃ (alumina): 0.21% by weight, ZrO ₂ (zirconium dioxide): 0.12% by weight, and SrCO ₃ (cerium carbonate): 0.13% by weight.

The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (The phthalates or phosphates) are sufficiently stirred to form a ceramic slurry, and a high dielectric constant ceramic layer having a thickness of 2 to 5 μm is formed by coating, and then printed on a high dielectric constant ceramic layer. A nickel metal electrode to form a high dielectric constant ceramic electrode layer.

Examples 1-10: High dielectric constant ceramic materials consisting of a main phase material and an oxide additive having a k value of 2,950. The main phase material is BaTiO ₃ , the molar ratio of Ba/Ti is 1.01, the particle size (D ₅₀ ) is 0.45 μm, and the oxide additive composition is based on 100% by weight of the main phase BaTiO ₃ . Including: BaCO ₃ (cerium carbonate): 2.70% by weight, MoO ₃ (molybdenum trioxide): 0.04% by weight, SiO ₂ (cerium oxide): 0.48% by weight, Y ₂ O ₃ (cerium oxide): 0.54% by weight, MgO (magnesium oxide): 0.04% by weight, MnCO ₃ (manganese carbonate): 0.25% by weight, Sm ₂ O ₃ (antimony trioxide): 0.05% by weight, Dy ₂ O ₃ (yttria): 0.28% by weight.

The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (The phthalates or phosphates) are sufficiently stirred to form a ceramic slurry, and a high dielectric constant ceramic layer having a thickness of 2 to 5 μm is formed by coating, and then printed on a high dielectric constant ceramic layer. A nickel metal electrode to form a high dielectric constant ceramic electrode layer.

The high dielectric constant ceramic structural layer described above is made of a high dielectric constant ceramic material. The following is an example of a composition of a low dielectric constant ceramic material and a method for fabricating a low dielectric constant ceramic structural layer:

Embodiment 2-1: The composition of the low dielectric constant ceramic material includes the common phase material and other oxide additives, the k value is 10, and the total weight of the low dielectric constant ceramic material is set to 100% by weight, and the common phase material is first: CaCO ₃ (calcium carbonate): 11.38% by weight, MgO (magnesium oxide): 0.05% by weight, TiO ₂ (titanium dioxide): 10.07% by weight, ZrO ₂ (zirconium dioxide): 6.74% by weight, HfO ₂ (cerium oxide) 0.15 wt%, added to water and added with a dispersant, thoroughly stirred, dried, and then calcined at 1100 ° C to 1350 ° C to form a phase, and the particle size (D ₅₀ ) of the common phase material was controlled to be 0.33 μm. And adding other oxide additives to the common phase material, the oxide additive components are as follows: BaCO ₃ (cerium carbonate): 7.97 wt%, CaCO ₃ (calcium carbonate): 19.65 wt%, MgO (magnesium oxide): 11.15 wt%, ZnO (zinc oxide): 5.83 wt%, SiO ₂ (ceria): 26.58 wt%, and Al ₂ O ₃ (alumina): 0.18 wt%. The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (The phthalic acid ester or the phosphate ester) is sufficiently stirred to form a ceramic slurry, and a low dielectric constant ceramic layer is formed by coating, and the low dielectric constant ceramic layer has a thickness of 3 to 6 μm.

Embodiment 2-2: The composition of the low dielectric constant ceramic material includes a common phase material and an oxide additive, the k value is 30, and the total weight of the low dielectric constant ceramic material is set to 100% by weight, and the common phase material: CaCO is first used. ₃ (calcium carbonate): 22.05% by weight, SrCO ₃ (cerium carbonate): 20.4% by weight, MgO (magnesium oxide): 0.07% by weight, TiO ₂ (titanium dioxide): 1.36% by weight, ZrO ₂ (zirconium dioxide): 51.3 % by weight, HfO ₂ (cerium oxide): 1.53% by weight, added to water and added with a dispersing agent, fully stirred, dried, and then calcined at 1100 ° C ~ 1350 ° C to form a phase, the powder size of the common phase material The (D ₅₀ ) range was controlled at 0.34 μm. And adding an oxide additive to the common phase material, the oxide additive component is as follows: BaCO ₃ (cerium carbonate): 1.21% by weight, MnCO ₃ (manganese carbonate): 0.67% by weight, SiO ₂ (cerium oxide): 1.41% by weight . The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (The phthalic acid ester or the phosphate ester) is sufficiently stirred to form a ceramic slurry, and a low dielectric constant ceramic layer is formed by coating, and the low dielectric constant ceramic layer has a thickness of 3 to 6 μm.

Embodiment 2-3: The composition of the low dielectric constant ceramic material includes a common phase material and an oxide additive, the k value is 31, and the total weight of the low dielectric constant ceramic material is set to 100% by weight, and the common phase material is first: CaCO ₃ (calcium carbonate): 21.42% by weight, SrCO ₃ (cerium carbonate): 21.31% by weight, MgO (magnesium oxide): 0.91% by weight, TiO ₂ (titanium dioxide): 1.69 % by weight, ZrO ₂ (zirconium dioxide): 50.15 % by weight, HfO ₂ (cerium oxide): 1.23% by weight, added to water and added with a dispersing agent, fully stirred, dried, and then calcined at 1100 ° C ~ 1350 ° C to form a phase, the powder size of the common phase material The (D ₅₀ ) range was controlled at 0.41 μm. And adding an oxide additive to the common phase material, the oxide additive component is as follows: MnCO ₃ (manganese carbonate): 0.9% by weight, SiO ₂ (cerium oxide): 1.91% by weight, Ta ₂ O ₅ (bisanthine pentoxide) : 0.11% by weight, Y ₂ O ₃ (cerium oxide): 0.1% by weight. The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (The phthalic acid ester or the phosphate ester) is sufficiently stirred to form a ceramic slurry, and a low dielectric constant ceramic layer is formed by coating, and the low dielectric constant ceramic layer has a thickness of 3 to 6 μm.

Embodiment 2-4: The composition of the low dielectric constant ceramic material comprises a common phase material and an oxide additive, the k value is 65, and the total weight of the low dielectric constant ceramic material is set to 100% by weight, and the common phase material is first: CaCO ₃ (calcium carbonate): 21.97% by weight, SrCO ₃ (cerium carbonate): 20.32% by weight, TiO ₂ (titanium dioxide): 11.16% by weight, ZrO ₂ (zirconium dioxide): 43.5% by weight, HfO ₂ (cerium oxide) : 0.97 wt%, added to water and added with a dispersing agent, thoroughly stirred, dried, and then calcined at 1100 ° C to 1350 ° C to form a phase, the particle size (D ₅₀ ) of the common phase material is controlled to be 0.51 μm. An oxide additive was added to the common phase material, and the oxide additive component was as follows: MnCO ₃ (manganese carbonate): 1.14% by weight, SiO ₂ (cerium oxide): 0.94% by weight. The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (The phthalic acid ester or the phosphate ester) is sufficiently stirred to form a ceramic slurry, and a low dielectric constant ceramic layer is formed by coating, and the low dielectric constant ceramic layer has a thickness of 3 to 6 μm.

Embodiment 2-5: The composition of the low dielectric constant ceramic material comprises a common phase material and an oxide additive, the k value is 70, and the total weight of the low dielectric constant ceramic material is set to 100% by weight, and the common phase material is first: CaCO ₃ (calcium carbonate): 35.85% by weight, MgO (magnesium oxide): 0.15% by weight, TiO ₂ (titanium dioxide): 14.86% by weight, ZrO ₂ (zirconium dioxide): 45.98% by weight, HfO ₂ (cerium oxide): 1.15% by weight, added to water and added a dispersing agent, fully stirred, dried, and then calcined at 1100 ° C ~ 1350 ° C to form a phase, the particle size (D ₅₀ ) of the common phase material is controlled to 0.54 μm. And adding an oxide additive to the common phase material, the oxide additive component is as follows: MnCO ₃ (manganese carbonate): 1.3% by weight, SiO ₂ (cerium oxide): 0.59% by weight, Y ₂ O ₃ (yttrium oxide): 0.12 weight%. The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (The phthalic acid ester or the phosphate ester) is sufficiently stirred to form a ceramic slurry, and a low dielectric constant ceramic layer is formed by coating, and the low dielectric constant ceramic layer has a thickness of 3 to 6 μm.

Embodiment 2-6: The composition of the low dielectric constant ceramic material comprises a common phase material and an oxide additive, the k value is 81, and the total weight of the low dielectric constant ceramic material is set to 100% by weight, and the common phase material is first: CaCO ₃ (calcium carbonate): 23.21% by weight, SrCO ₃ (cerium carbonate): 20.98% by weight, TiO ₂ (titanium dioxide): 14.15% by weight, ZrO ₂ (zirconium dioxide): 38.16% by weight, HfO ₂ (cerium oxide) : 1.02% by weight, added to water and added with dispersant, fully stirred, dried, and then calcined at 1100 ° C ~ 1350 ° C, the particle size (D ₅₀ ) of the common phase material is controlled at 0.56 μ m . An oxide additive was added to the common phase material, and the oxide additive component was as follows: MnCO ₃ (manganese carbonate): 1.29 wt%, SiO ₂ (cerium oxide): 1.19 wt%. The above composition is mixed with an appropriate amount of a dispersing agent (anionic surfactant) in an organic solvent (toluene and an alcohol mixed solvent), and after being dispersed by grinding, a binder (polyvinyl butyral resin) and a plasticizer are added. (The phthalates or phosphates) are sufficiently stirred to form a ceramic slurry, and a low dielectric constant ceramic layer is formed by coating, and the low dielectric constant ceramic layer has a thickness of 3 to 6 μm .

In addition, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and is simply equivalent according to the technical idea disclosed in the scope of the present invention and the contents of the description of the invention. Variations and modifications should still fall within the scope of the present invention. For example, the starting materials of BaO may be BaCO ₃ , BaC ₂ O ₄ , Ba(C ₂ H ₅ OO) _{2 ,} etc.; the initiation of Mn ₂ CO ₃ The substance may be MnO ₂ or the like.

Next, the high dielectric constant ceramic layer, the high dielectric constant electrode layer, the low dielectric constant ceramic layer and the low dielectric constant electrode layer obtained by the above-described production method are combined by using different interlaced layers to form a laminated electronic ceramic component, including: At least one cover layer, at least one reaction layer, and at least one nickel metal electrode layer. Wherein, the cover layer is a high dielectric constant ceramic layer or a low dielectric constant ceramic layer, and the reaction layers are alternately laminated between the cover layers or the cover layer side, and the reaction layer is a high dielectric constant ceramic structure layer or a low dielectric constant ceramic. The structural layer, the nickel metal electrode layer is located at the staggered stacking position of the reaction layer.

Referring to FIGS. 2 to 5C, the laminated electronic ceramic component mainly includes a first cover layer 100, a second cover layer 200, a reaction layer 300 interleaved between the first cover layer 100 and the second cover layer 200, and a reaction layer. 300 staggered laminated nickel metal electrode layer 400, the first covering layer 100 is a high dielectric constant ceramic layer 501 or a low dielectric constant ceramic layer 601, and the second covering layer is a high dielectric constant ceramic layer 501 or a low dielectric constant The ceramic layer 601, the reaction layer 300 is a high dielectric constant ceramic structure layer 500, a low dielectric constant ceramic structure layer 600 or a high dielectric constant ceramic structure layer 500 and a low dielectric constant ceramic structure layer 600.

Table I

Please refer to Table 1, which is a cross-stacked structure type list of a first cladding layer, a second cladding layer and a reaction layer of the laminated electronic ceramic component, wherein the high dielectric constant ceramic structural layer 500 comprises a high dielectric constant ceramic layer 501 and The high dielectric constant electrode layer 502, the low dielectric constant ceramic structure layer 600 includes a low dielectric constant ceramic layer 601 and a low dielectric constant electrode layer 602, and the high dielectric constant electrode layer 502 is printed with a nickel metal electrode layer 400 on the surface. The high dielectric constant ceramic layer 501, the low dielectric constant electrode layer 602 is a low dielectric constant ceramic layer 601 on which a nickel metal electrode layer 400 is printed, and the nickel metal electrode layer 601 is continuous, discontinuous or floating.

The laminated type X structure is a first cap layer 100 and a second cap layer 200 is a high dielectric constant ceramic layer 501, and the reactive layer 300 is a staggered laminated high dielectric constant ceramic structure layer 500.

Wherein, the laminated type A structure is that the first cover layer 100 is a high dielectric constant ceramic layer 501, the second cover layer 200 is a low dielectric constant ceramic layer 601, and the reaction layer 300 is a high dielectric constant ceramic of a staggered laminate. Structure layer 500.

The laminated type B structure first first layer 100 and the second cover layer 200 are low dielectric constant ceramic layers 600, and the reaction layer 300 is a high dielectric constant ceramic structure layer 500 which is staggered.

Wherein, the stacked type C and D structures are the first cover layer 100 and the second cover layer 200 are low dielectric constant ceramic layers 600, and the reaction layer 300 is a high dielectric constant ceramic structure layer 500 and a low dielectric constant. The ceramic structural layers 600 are alternately laminated.

After the first cover layer 100, the second cover layer 200 and the reaction layer 300 are interlaced, the terminal electrode is completed by a process such as Dipping, Curing, Plating, etc. Measuring the difference in component characteristics, staggering the laminated structure through different dielectric material components and components, The electrical properties obtained by sintering are shown. Compared with a laminated capacitor element of a single material (see Table 2 - Stacked form of X), a laminated capacitor element of two different materials is integrated, in terms of electrical characteristics, in addition to maintaining the same capacitance value level, the dissipation factor Insulation resistance, breakdown voltage and piezoelectric characteristics (electrostrictive) are significantly improved through different laminate designs. The components fabricated by co-sintering were analyzed by ultrasonic scanning (Scanning Acoustic Microscopy) (as shown in Table 2), and the structural defects of the components were observed with a sample number of 3000 components per set of conditions, and it was found that no internal defects existed. The invention co-fires two or more material systems under a reducing atmosphere, and can be completely realized in the production of electronic ceramic components.

Table II

To sum up, this case is not only innovative in terms of technical thinking, but also has the effect of the traditional structure that is not in use. It has fully complied with the statutory new patent requirements of novelty and progressiveness, and applied for it according to law. I urge you to approve this article. The new type of patent application, to encourage creation, to the sense of virtue.

S01~S02‧‧‧Step process

S021~S024‧‧‧Step procedure

Claims (10)

A pressureless co-sintering method for laminated electronic ceramic components, the steps comprising: (a) a dielectric constant (k value) greater than 1500 or higher high dielectric constant perovskite structural ceramic structural layer and a low dielectric having a k value of less than 100 a constant perovskite structure ceramic structure layer is interlaced to form a laminated electronic ceramic component; and (b) a laminated electronic ceramic component is introduced at 1150 ° C to 1350 ° C while introducing a mixture of moisture, nitrogen and hydrogen, and reducing atmosphere 10 ^- Co-sintering was carried out in a ⁶ ~ 10 ^-20 atm environment. A laminated electronic ceramic component produced according to the method of claim 1, comprising: (a) at least one cap layer, the cap layer being a high dielectric constant ceramic layer or a low dielectric constant ceramic layer; (b) at least one reaction a layer, the reaction layer is interlaced between the cover layers or the cover layer side, the reaction layer is a high dielectric constant ceramic structure layer or a low dielectric constant ceramic structure layer; and (c) at least one nickel metal electrode layer The nickel metal electrode layer is located at a position where the reaction layers are staggered. The multilayer electronic ceramic component according to claim 2, wherein the high dielectric constant ceramic structural layer comprises a high dielectric constant ceramic layer and a high dielectric constant electrode layer, and the low dielectric constant ceramic structural layer comprises a low dielectric constant ceramic layer and Low dielectric constant electrode layer. The laminated electronic ceramic component according to claim 3, wherein the high dielectric constant electrode layer is a high dielectric constant ceramic layer having a surface of a nickel metal (or nickel metal alloy) electrode pattern, and the low dielectric constant electrode layer is a surface application layer. A low dielectric constant ceramic layer of a nickel metal (or nickel metal alloy) electrode pattern. The laminated electronic ceramic component of claim 3 or 4, wherein the nickel metal electrode pattern is a continuous, discontinuous or floating pattern. The laminated electronic ceramic component according to claim 2, wherein the composition of the high dielectric constant ceramic layer comprises a main phase material and an oxide additive, and the main phase material is Ba _x Ti _y O ₃ (barium titanate), Ba (钡) / Ti (titanium) The molar ratio (x / y) is between 0.99 and 1.06, and the powder of the main phase material has an average particle size (D ₅₀ ) ranging from 0.1 to 0.5 μm. The laminated electronic ceramic component according to claim 6, which is based on 100% by weight of BaTiO ₃ (barium titanate), wherein the composition of the oxide additive comprises: 0.32 to 2.70 wt% of barium carbonate (BaCO ₃ ), 0 to 0.06 Wt% molybdenum trioxide (MoO ₃ ), 0.20~0.55wt% cerium oxide (SiO ₂ ), 0.17~0.72wt% yttria (Y ₂ O ₃ ), 0.04~0.34wt% magnesia (MgO), 0~ 0.07wt% bismuth pentoxide (Nb ₂ O ₅ ), 0.11~0.28wt% manganese carbonate (MnCO ₃ ), 0~1.61wt% yttrium oxide (Yb ₂ O ₃ ), 0~0.51wt% alumina (Al ₂ O ₃ ), 0~0.50wt% calcium carbonate (CaCO ₃ ), 0~0.21wt% zirconium dioxide (ZrO ₂ ), 0~0.05wt% antimony trioxide (Sm ₂ O ₃ ), 0~0.28wt% Yttrium oxide (Dy ₂ O ₃ ), 0-0.10wt% titanium dioxide (TiO ₂ ), 0-0.04wt% vanadium pentoxide (V ₂ O ₅ ), O~0.13wt% strontium carbonate (SrCO ₃ ) and 0~ 0.23 wt% tin oxide (SnO). The laminated electronic ceramic component according to claim 2, wherein the composition of the low dielectric constant ceramic layer comprises a common phase material and an oxide additive, and the common phase material has the structural formula [(Ca _x Sr _1-xy Mg _y )O] _m [(Ti _w Zr _1-wz Hf _z )O ₂ ], wherein the molar ratio of each element is: 0.65<x≦1, 0≦y<0.05, 0<w<0.74, 0<z<0.02, 0.95 ≦m≦ 1.15, the common phase material has a powder average particle size (D ₅₀ ) ranging from 0.3 to 0.6 μm. The laminated electronic ceramic component according to claim 8, wherein the composition of the low dielectric constant ceramic layer is selected from the group consisting of calcium carbonate (CaCO ₃ ), strontium carbonate (SrCO ₃ ), barium carbonate (BaCO ₃ ), and magnesium oxide ( MgO), titanium dioxide (TiO ₂ ), zirconium dioxide (ZrO ₂ ), zinc oxide (ZnO), manganese carbonate (MnCO ₃ ), cerium oxide (SiO ₂ ), hafnium oxide (HfO ₂ ), antimony pentoxide At least one material selected from the group consisting of (Ta ₂ O ₅ ), yttrium oxide (Y ₂ O ₃ ), and alumina (Al ₂ O ₃ ). The laminated electronic ceramic component according to claim 8, wherein the composition of the low dielectric constant ceramic layer (total content is 100% by weight) comprises: 21.42 to 35.85% by weight of calcium carbonate (CaCO ₃ ), 0 to 21.31% by weight of carbonic acid锶(SrCO ₃ ), 0~7.97wt% barium carbonate (BaCO ₃ ), 0~11.20wt% magnesium oxide (MgO), 1.36~14.86wt% titanium dioxide (TiO ₂ ), 6.74~51.30wt% zirconium dioxide (ZrO ₂ ), 0~5.83wt% zinc oxide (ZnO), 0~1.30wt% manganese carbonate (MnCO ₃ ), 0.59~26.58wt% cerium oxide (SiO ₂ ), 0.16~1.53wt% cerium oxide (HfO ₂ ), 0 to 0.11 wt% of tantalum pentoxide (Ta ₂ O ₅ ), 0 to 0.12 wt% of yttrium oxide (Y ₂ O ₃ ), and 0 to 0.18 wt% of alumina (Al ₂ O ₃ ).