Ceramic electronic components and circuit boards containing them

Abstract

This invention provides a ceramic electronic component comprising: a ceramic body and two first terminal electrodes. The ceramic body comprises a plurality of ceramic sublayers and a plurality of internal electrodes alternately stacked within the ceramic body; the two first terminal electrodes respectively cover at least one end face of the ceramic body and are electrically connected to the internal electrodes. The ceramic sublayers are formed by composition (A), and the first terminal electrodes are formed by composition (B); composition (A) comprises: a main powder material and a glass material; wherein, after undergoing a sintering process at 880°C, the contact angle between the glass material and the Cu / CuaO substrate is not greater than 20°, α=1 or 2; composition (B) comprises: copper powder, resin, and electrode paste solvent, and based on the total weight of composition (B), composition (B) contains no more than 3 wt% glass material. This invention also provides a circuit board comprising the aforementioned ceramic electronic component.

Description

Ceramic electronic components and circuit boards containing them Technical Field

[0001] This invention relates to a ceramic electronic component and a circuit board comprising said ceramic electronic component. Prior Technology

[0002] With the advent of the 5G high-frequency communication era, electronic products are developing towards lighter weight, more multifunctionality, higher reliability, and higher efficiency. Therefore, higher demands are placed on the integrated circuit (IC) and packaging technologies of electronic products. Packaging technology directly affects the high-speed transmission, power consumption, complexity, reliability, and cost of electronic products and ICs, thus becoming a focus of attention and research in the electronics field. Among these, passive components, although they do not amplify signal strength or generate energy, play an indispensable role in power supply applications such as voltage regulation and current limiting, signal processing applications such as filtering, coupling, and blocking, and circuit protection applications such as overvoltage protection, overcurrent protection, and surge protection. Specific passive components include, but are not limited to, resistors, capacitors, and inductors. Low-temperature co-fired ceramic (LTCC) technology essentially integrates low-dielectric-constant, high-frequency, and low-loss ceramic materials with conductive circuitry (typically high-conductivity, low-melting-point materials such as gold (Au), silver (Ag), and copper (Cu) as conductors) onto the same substrate and sintersects them together at a low temperature (usually below 1120°C). Because of its combination of low-loss materials and the ability to achieve complex wiring patterns on multilayer ceramic substrates, it integrates multiple passive components into a single module, offering significant advantages in developing high-frequency, high-performance electronic components. Therefore, LTCC has become the most promising technology for integrating high-frequency passive components.

[0003] LTCC ceramic materials are microstructures containing a main crystalline phase, crystal defects such as grain boundaries, pores, impurities, secondary crystalline phases, and glass sintering aids. These microstructure characteristics significantly affect the dielectric properties of the ceramic material. To meet the requirements of full 5G applications and extend the operating frequency band of ceramic electronic components to the millimeter-wave range, LTCC materials must simultaneously possess appropriate dielectric constants, low dissipation factors (Df), and a temperature coefficient of resonant frequency (τf) approaching zero. Furthermore, they must also meet requirements such as lowering the sintering temperature and increasing the density of the resulting sintered body. However, currently, ceramic materials that meet the dielectric properties of LTCC require high sintering temperatures (greater than 1000°C). For example, US Patent 5599757A discloses an NPO (Negative-Positive-Zero) type dielectric ceramic composition, which mainly contains about 91 wt% to 94.5 wt% of a calcined matrix mixture (BaTiO3, TiO2, ZrO2, and SiO2 in specific content ranges), about 6.0 wt% to 7.5 wt% of a low-melting-point glass sintering aid, about 0 wt% to 0.25 wt% of Mn(NO3)2, and about 0 wt% to 1.5 wt% of SiO2. Multi-Layer Ceramic Capacitors (MLCCs) made from the dielectric ceramic composition can produce low Df (less than or equal to 0.010%) under a 1.0 Vrms signal and a 1 MHz test frequency, and at 5 A high Q value (over 5000) is generated at a GHz test frequency. However, the aforementioned dielectric ceramic composition still needs to be sintered at a temperature higher than the melting point of pure copper (around 1120°C), making it difficult to apply to copper-containing co-firing processes.

[0004] To address the aforementioned issues, US10562809 B2 discloses a dielectric material that exhibits a quality factor (Q value) greater than 1000, a dielectric constant (K value) of approximately 8, and a sintering temperature below 1100°C when measured at 10 GHz. Prior to sintering, the dielectric material comprises 10 wt% to 95 wt% silicon dioxide powder and 5 wt% to 90 wt% glass frit with an average size of 1 to 90 wt% ranging from 0.5 micrometers (μm) to 30 μm; wherein the glass frit contains a specific content of a specific component system of glass composition, and the total amount of Li₂O + Na₂O + K₂O must be 0.3 to 30 moles of the glass frit. However, using amorphous silicon dioxide powder leads to a decrease in the Q value, degrading high-frequency transmission characteristics, and the dielectric material requires complex manufacturing processes, hindering its commercial viability.

[0005] On the other hand, the terminal electrodes of LTCCs are usually made by applying electrode paste, and conventional electrode pastes generally contain conductive metals, glass powder with a low softening temperature, resin, and solvents. Currently, the conductive metals used in high-frequency components for low-temperature co-fired electronic components and modules are mainly composed of silver or silver-palladium (Ag-Pd) alloys, and both Ag and Pd are precious metals.

[0006] Generally, the glass powder with a low softening temperature has a particle size between 1 μm and 5 μm. Its main purpose is to provide a liquid phase during sintering, allowing the conductive metal to sinter into a metal layer at a lower temperature and react with the ceramic body at the interface to form a bond, thereby improving the adhesion between the two. However, if the glass powder particle size is too large, it tends to aggregate at the interface, resulting in poor connection between the inner electrode and the end electrode (also known as the outer electrode). Furthermore, the glass phase formed by the aforementioned glass powder is easily expelled, leading to poor solderability when the second end electrode is subsequently formed by electroplating, or segregation into the copper layer causing increased resistance. Moreover, the aforementioned glass powder may also generate bubbles during curing, resulting in pores in the obtained end electrode or separation of the inner and outer electrodes, increasing the resistance of the ceramic electronic component containing it and negatively impacting its conductivity and transmission properties. In recent years, driven by the increasing demand for high-frequency components, as well as the need for high performance and high reliability, it has become an important issue to improve the conductivity of ceramic electronic components to reduce the reliability of components due to transmission loss and heat generation, and to improve the interfacial bonding between the terminal electrode and the ceramic body to avoid the failure of ceramic electronic components due to the peeling of the terminal electrode during use.

[0007] Furthermore, from a product reliability perspective, silver migration through dielectric materials increases the risk of material failure. Ion migration typically occurs when voltage is applied in high-humidity environments, causing the anode metal to ionize and migrate to the cathode. The cathode metal then undergoes the same process, potentially leading to a short circuit. In addition, the price of precious metals is increasing year by year, keeping manufacturing costs high. Therefore, developing base metal electrode paste that combines low cost and high reliability for forming terminal electrodes is also an important research focus. Summary of the Invention

[0008] In view of the technical defects of the prior art, the purpose of this invention is to provide a ceramic electronic component that can avoid the generation of bubbles in the electrode paste forming the external electrode during the firing process, improve the bonding and conductivity between the external electrode formed therefrom and the ceramic body, and reduce the problem of external electrode peeling off during use, thereby improving the yield of the ceramic electronic component.

[0009] Another objective of this invention is to provide a ceramic electronic component that avoids the problem of glass overflowing from the predetermined coating surface during the sintering process of the electrode paste forming the external electrode, thereby significantly reducing the occurrence of poor solderability when forming the second external electrode.

[0010] The purpose of this invention is to provide a ceramic electronic component that uses copper-containing terminal electrodes (i.e., external electrodes) instead of precious metal-containing terminal electrodes, thereby reducing production costs and increasing the diversity and development potential of subsequent product applications.

[0011] To achieve the aforementioned objective, this invention provides a ceramic electronic component comprising: a ceramic body having a first end face and a second end face opposite to each other; and two first end electrodes; the ceramic body comprising: a plurality of ceramic sublayers and a plurality of internal electrodes; wherein the ceramic sublayers and the internal electrodes are alternately stacked within the ceramic body; the two first end electrodes respectively cover the first end face and the second end face of the ceramic body and are electrically connected to the internal electrodes. The ceramic electronic component is made from a raw material composition comprising composition (A) and composition (B). Composition (A) comprises a main powder material and a glass material. The total weight of the main powder material and the glass material is 100 parts by weight, and the content of the glass material is 5 to 20 parts by weight. The main powder material comprises barium titanate microwave dielectric oxide, calcium zirconate microwave dielectric oxide, or a combination thereof. After the glass material undergoes a sintering process at 880°C, its contact angle with the Cu / CuaO substrate is not greater than 20°, and a = 1 or 2. Composition (B) comprises copper powder, resin, and electrode paste solvent. Based on the total weight of composition (B), composition (B) contains no more than 3 wt% glass material. The ceramic sublayers of the ceramic body are formed by composition (A), and the two first terminal electrodes are formed by composition (B).

[0012] In some embodiments, two adjacent inner electrodes in the ceramic body are respectively connected to a first end face and a second end face of the ceramic body; these inner electrodes contain a base metal. That is, each inner electrode is in contact with only one of the two first end electrodes.

[0013] In some embodiments, each inner electrode in the ceramic body is connected to both a first end face and a second end face of the ceramic body; these inner electrodes comprise a base metal. That is, each inner electrode is in contact with the two first end electrodes.

[0014] Preferably, the aforementioned base metal may include copper. When the aforementioned base metal is copper, the ceramic electronic component containing the copper internal electrode may have the advantages of suppressing ion migration and having a lower cost advantage compared to silver.

[0015] In some embodiments, each end electrode may have a double-layer structure, meaning the ceramic electronic component may further include two second end electrodes formed on the outer surfaces of the two first end electrodes; wherein the two second end electrodes contain nickel. Specifically, the first end electrodes respectively cover opposite end faces (e.g., the first end face and the second end face) of the ceramic body and are electrically connected to the inner electrodes, while the second end electrodes are formed on the outer surfaces of the first end electrodes, and the two second end electrodes are formed by electroplating or sputtering, but are not limited thereto. The aforementioned second end electrodes provide a protective function, thus further improving the reliability of the ceramic electronic component (e.g., but not limited to, a multilayer connector).

[0016] In some embodiments, the ceramic electronic component may further include two solder layers, which are respectively formed on the outer surfaces of the two second terminal electrodes; wherein the two solder layers contain tin. That is, each second terminal electrode is formed between a first terminal electrode and a solder layer. Specifically, the two solder layers are formed by electroplating or sputtering, but are not limited thereto.

[0017] This invention also provides a ceramic electronic component, comprising: a ceramic body having a first end face; two first end electrodes disposed on the first end face of the ceramic body; and two conductor connectors, each disposed in the ceramic body and respectively in contact with the two first end electrodes. The ceramic body comprises: a plurality of ceramic sublayers and a plurality of inner electrodes; wherein the ceramic sublayers and the inner electrodes are alternately stacked within the ceramic body; each inner electrode is connected to the two conductor connectors and electrically connected to the two first end electrodes; wherein the ceramic electronic component is made from a raw material composition comprising the aforementioned composition (A) and the aforementioned composition (B), wherein the ceramic sublayers of the ceramic body are formed by the aforementioned composition (A), and the two first end electrodes are formed by the aforementioned composition (B).

[0018] Specifically, the conductor connector may be a through-hole conductor, but is not limited thereto.

[0019] In some embodiments, the aforementioned ceramic electronic component may further include two second terminal electrodes and two flux layers; wherein the two second terminal electrodes are respectively formed on the outer surface of the two first terminal electrodes; wherein the two second terminal electrodes contain nickel; wherein the two flux layers are respectively formed on the outer surface of the two second terminal electrodes; wherein the two flux layers contain tin. That is, each second terminal electrode is formed between a first terminal electrode and a flux layer.

[0020] In this invention, the ceramic electronic component can be applied to embedded (also known as embedded) ceramic electronic components or surface-mount ceramic electronic components, but is not limited thereto. Specifically, when the ceramic electronic component includes the two first terminal electrodes but does not include the two second terminal electrodes and / or the two solder layers, the ceramic electronic component is suitable for application in the aforementioned embedded ceramic electronic components; on the other hand, when the ceramic electronic component includes the two first terminal electrodes, the second terminal electrodes, and the two solder layers, the ceramic electronic component is suitable for application in the aforementioned surface-mount ceramic electronic components.

[0021] This invention achieves the following characteristics by simultaneously controlling the composition (A) forming the ceramic body and the composition (B) forming the first end electrode: composition (A) contains a specific type of main powder material and a glass material with high affinity for copper and / or cuprous oxide; and composition (B) uses copper powder instead of Ag commonly used in the prior art and controls the glass powder content. Therefore, the copper powder in composition (B) can generate cuprous oxide (Cu2O) during the sintering and debinding stages. Furthermore, because the glass material in composition (A) has good affinity for cuprous oxide, even if composition (B) does not contain a sufficient amount of low-softening-temperature glass powder, the composition (A) can still achieve the desired effect. The trace amounts of glass material, due to its wettability and capillary action, spread uniformly on the copper powder surface to form a liquid-phase thin film layer. This allows for dense sintering of the copper electrode (first end electrode) with less glass material, avoiding many problems caused by glass powder aggregation at the interface during the sintering process of previous electrode pastes. This improves the bonding strength between the ceramic body and the first end electrode, reduces the risk of water vapor intrusion and failure due to breakage of the ceramic electronic component, and, because the first end electrode contains very little glass after sintering, it has low resistivity, thereby improving the conductivity of the ceramic electronic component and ensuring good high-frequency characteristics. If a second end electrode is subsequently formed, its thickness can be made uniform and the layer continuous, thus preventing sulfidation breakage caused by the intrusion of sulfiding gases (such as H2S, SO2, etc.) when using the ceramic electronic component in a sulfur-containing environment. Furthermore, by using copper powder instead of the conventional silver powder as the conductive powder for the first terminal electrode, not only can it have high reliability and avoid the risk of short circuits caused by ion migration, but it can also significantly reduce production costs, which is conducive to the diversification and development potential of subsequent product applications.

[0022] In this invention, the glass material in composition (B) may be the same as or different from the glass material in composition (A).

[0023] Preferably, the composition (B) substantially does not contain glass material. The foregoing phrase "substantially does not contain" means that, based on the total weight of the composition (B), the composition (B) contains no more than 1 wt% glass material. More preferably, the composition (B) contains no more than 0.5 wt% glass material; even more preferably, the composition (B) contains 0 wt% glass material (i.e., completely free of glass material).

[0024] Preferably, after the glass material undergoes a firing process at 880°C, the contact angle between it and the Cu / CuaO substrate (a=1 or 2) is no greater than 15°.

[0025] Preferably, after the glass material undergoes a sintering process at 940°C, the contact angle between it and the Cu / CuaO substrate (a=1 or 2) is not greater than 10°; more preferably, after the glass material undergoes a sintering process at 940°C, the aforementioned contact angle is not greater than 5°.

[0026] Preferably, the glass material in the composition (A) contains Cu2O; more preferably, the glass material in the composition (A) contains 0.5 wt% to 3 wt% Cu2O.

[0027] In some embodiments, the barium titanate microwave dielectric oxide in composition (A) may comprise: BaTixO2x+1, wherein x = 3.5 to 5.0, but is not limited thereto. Preferably, when the barium titanate microwave dielectric oxide in composition (A) is of the aforementioned specific type, the glass material in composition (A) may comprise: BaO-ZnO-B2O3-CaO-Al2O3-SiO2-Bi2O3-Cu2O, Na2O-CaO-BaO-ZnO-B2O3-SiO2-Cu2O, or a combination thereof. In some embodiments, the barium titanate microwave dielectric oxide in composition (A) is BaTixO2x+1, and x = 4 (the barium titanate microwave dielectric oxide is BaTi4O9). In some embodiments, the barium titanate microwave dielectric oxide in the composition (A) is BaTixO2x+1, and x=4.5 (the barium titanate microwave dielectric oxide is BaTi4.5O10, which can also be represented as Ba2Ti9O20).

[0028] In some embodiments, the composition (A) may further include a dopant selected from at least one of the group consisting of MnCO3, CaCO3, SrCO3, ZrO2, Dy2O3, and BaWO4; wherein, based on the mole number of the main powder material, the content of the dopant may be from 0.45 mole% to 7.5 mole%, but is not limited thereto.

[0029] Specifically, when the barium titanate microwave dielectric oxide is BaTixO2x+1 and x=4 (i.e., the barium titanate microwave dielectric oxide is BaTi4O9), the dopant is preferably any one of MnCO3, CaCO3, SrCO3, ZrO2, Dy2O3 or BaWO4, but is not limited thereto.

[0030] Furthermore, when the barium titanate microwave dielectric oxide is BaTixO2x+1 and x=4.5 (i.e., the barium titanate microwave dielectric oxide is Ba2Ti9O20), the dopant is preferably MnCO3, ZrO2, WO3, or SnO2, but is not limited to these.

[0031] In other embodiments, the calcium zirconate-based microwave dielectric oxide in composition (A) may comprise (SraCa1-a)(Zr1-bMnb)O3, wherein 0 ≤ a < 0.2; 0 ≤ b < 0.3, but is not limited thereto. Preferably, when the calcium zirconate-based microwave dielectric oxide in composition (A) is of the aforementioned specific type, the glass material in composition (A) may comprise: MnO-MgO-Al2O3-SiO2-Cu2O, Li2O-MnO-MgO-Al2O3-SiO2-Cu2O, or a combination thereof.

[0032] In some embodiments, the composition (A) may also contain a dispersant, a binder, a plasticizer, an organic solvent, or a combination thereof.

[0033] Preferably, the composition (A) may further comprise the dispersant; for example, the dispersant may comprise a modified acrylic copolymer having pigment-affinity groups; for example, the dispersant may be a commercially available product (manufacturer: BYK, model: DISPERBYK-2001), but is not limited thereto. Preferably, based on the total weight of the composition (A) (100 wt%), the content of the dispersant may be from 1 wt% to 3 wt%, but is not limited thereto.

[0034] Preferably, the composition (A) may further comprise the adhesive; for example, the adhesive may comprise, but is not limited to, polyvinyl butyral (PVB) resins, (meth)acrylic resins, or combinations thereof. Preferably, the content of the adhesive, based on the total weight of the composition (A), may be from 4 wt% to 12 wt%, but is not limited thereto.

[0035] Preferably, the composition (A) may further comprise the plasticizer; for example, the plasticizer may comprise phthalates (PAEs); specifically, the phthalates may comprise, but are not limited to, bis(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP), diisononyl phthalate (DINP), butyl benzyl phthalate (BBP), and di-isodecyl phthalate (DIDP). Preferably, the content of the plasticizer may be from 1 wt% to 5 wt% based on the total weight of the composition (A), but is not limited to this.

[0036] Preferably, the composition (A) may further contain the organic solvent, allowing the composition (A) to form a slurry, which can be used to form a ceramic body by coating or by first forming a plurality of ceramic sublayers that can constitute the ceramic body, but is not limited thereto. Specifically, the organic solvent may contain toluene, ethanol, or a combination thereof, but is not limited thereto. Preferably, the organic solvent may be a combination of toluene and ethanol, and the weight ratio of toluene to ethanol may be 6:4 to 4:6; for example, the weight ratio of toluene to ethanol may be 5:5. Preferably, based on the total weight of the composition (A), the content of the organic solvent may be 28 wt% to 40 wt%, but is not limited thereto.

[0037] Preferably, the total weight of the main powder material, the dopant and the glass material is 50 wt% to 65 wt%, but not limited thereto, based on the total weight of the composition (A).

[0038] In some embodiments, the weight ratio of the copper powder to the resin in the composition (B) may be from 25:1 to 6:1, but is not limited thereto.

[0039] Optionally, the composition (B) can be dried at 120°C to form a green embryo with a green embryo density of 3.5 g / cm3 to 5.8 g / cm3, but not limited thereto.

[0040] Preferably, in the composition (B), the average particle size of the copper powder is from 0.1 μm to 12 μm, but is not limited thereto; the aforementioned average particle size is expressed as the particle size D50 measured by laser diffraction particle size distribution method. In some embodiments, the copper powder contained in the composition (B) may have different sizes; for example, the copper powder may simultaneously contain spherical copper metal particles with an average particle size of 0.5 μm to 5 μm and spherical or flake-shaped copper metal particles with an average particle size of 6 μm to 10 μm. When the particle size of the copper powder is within the aforementioned range, it can have better sintering activity and is less prone to severe powder agglomeration.

[0041] In this invention, the resin in composition (B) may comprise, but is not limited to, acrylic resins, ethyl cellulose resins, or combinations thereof. For example, the acrylic resin may be an acrylate such as poly(methyl acrylate), PMA, poly(ethyl acrylate), PEA, or derivatives thereof; or a methacrylate such as poly(methyl methacrylate), PMMA, poly(ethyl methacrylate), PEMA, or derivatives thereof, but is not limited thereto; the ethyl cellulose resin may be ethyl cellulose or derivatives thereof, but is not limited thereto. In some embodiments, polymethyl methacrylate may be used if subsequently coated onto the ceramic body by roller or dip coating; in other embodiments, ethyl cellulose may be used if subsequently coated onto the ceramic body by printing. The resin can uniformly disperse copper powder particles, giving the composition (B) better rheological properties during coating; however, during the drying process, it can also bind the copper powder particles together, giving the subsequently formed green body sufficient mechanical strength and preventing it from being damaged by collisions during the process, resulting in cracking or deformation.

[0042] In this invention, the electrode paste solvent in composition (B) may comprise alcohols, ethers, esters, or combinations thereof. For example, the alcohol may be terpineol, cyclohexanemethanol, benzyl alcohol, 2-ethyl-1-hexanol, 1-octanol, etc., but is not limited thereto; the ether may be ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether (also known as carbitol), etc., but is not limited thereto; the ester may be terpinyl dihydroacetate, terpinyl acetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate [2-(2-ethoxyethoxy)ethyl acetate], etc., but is not limited thereto.

[0043] Preferably, based on the total weight of the composition (B), the content of copper powder is 70 wt% to 80 wt%, the content of resin is 2.8 wt% to 10 wt%, and the content of electrode paste solvent is 15 wt% to 25 wt%, but not limited thereto.

[0044] Without affecting the overall effect of this invention, the composition (B) may also contain thixotropic agents, dispersants, defoamers, leveling agents, and other additives as needed. For example, the thixotropic agent may be polyamide wax, which can adjust the viscosity of the composition (B) to meet the application requirements of the first end electrode process; the dispersant may be polyether phosphate, which can adjust the viscosity of the composition (B) to meet the application requirements of the first end electrode process; the defoamer may be ethylene polymer, which can provide the composition (B) with the ability to defoam itself, improving the possibility of the composition (B) carrying air bubbles during the process; the leveling agent may be a silicone additive with alkyl aromatic groups, which can further improve the surface flatness of the composition (B) after application, but is not limited to this.

[0045] According to this invention, when preparing the composition (B), copper powder, resin, electrode paste solvent and / or the aforementioned excipients may be added and mixed in any order, simultaneously or sequentially, with the entire weight of the components added at once or in equal weights in several batches, and the composition (B) is prepared by stirring and dispersing until it is uniform.

[0046] In the manufacturing process of the ceramic electronic component, the composition (B) can be coated onto the opposite two end surfaces (i.e., the first end surface and the second end surface) of the ceramic body and then sintered to form the two first end electrodes of the ceramic electronic component. Specifically, the coating method can be any coating method known in the prior art, such as knife coating, dipping coating, rolling coating, printing coating, injection coating, etc.

[0047] Specifically, the viscosity of the composition (B) can be from 20 kCp to 165 kCp, but is not limited thereto. When the viscosity of the composition (B) is within the aforementioned range, it exhibits better operability and is less prone to appearance abnormalities, sagging, or sticking. In some embodiments, when the composition (B) is applied to the opposite end surfaces of the ceramic body by dip coating, the viscosity of the composition (B) is preferably 40 kCp to 80 kCp; when the composition (B) is applied to the opposite end surfaces of the ceramic body by roller coating, the viscosity of the composition (B) is preferably 25 kCp to 40 kCp; when the composition (B) is applied to the first end face or opposite end surfaces of the ceramic body by printing, the viscosity of the composition (B) is preferably 20 kCp to 165 kCp.

[0048] Specifically, there are no particular limitations on the aforementioned sintering temperature, but a preferred sintering temperature is 850°C to 950°C, which allows the obtained first end electrode to have a denser structure.

[0049] Preferably, the aforementioned calcination step can be carried out in a nitrogen atmosphere; specifically, the nitrogen atmosphere contains no more than 100 ppm of oxygen to avoid the formation of excessive or thick cuprous oxide on the surface of the obtained first end electrode, which would cause an unnecessary increase in resistivity and a decrease in equivalent series resistance (ESR).

[0050] In this invention, the ceramic electronic component may be a connector electronic component, a capacitor, but is not limited to these. For example, the ceramic electronic component may be a radio frequency (RF) multilayer ceramic capacitor (MLCC), a multilayer connector electronic component, etc., but is not limited to these.

[0051] Furthermore, unlike surface-mount ceramic components, the mounting method for embedded ceramic electronic components is as follows: First, a precise cavity must be pre-cut in the dielectric substrate (such as an insulating substrate composed of dielectric material), typically on the core layer of a printed circuit board (PCB). The size and position of this cavity perfectly match the size of the ceramic electronic component to be embedded. After the ceramic electronic component is placed, it is then fixed within the cavity using a special resin or molding polymer, filling all gaps. This step ensures that the ceramic electronic component will not move during subsequent processes and also avoids the formation of air bubbles. After the ceramic electronic component is fixed and filled, an additional PCB layer (such as prepreg) is stacked on top. Then, the entire structure is placed in a thermopressor for lamination under high temperature and pressure, forming a robust whole. In addition, the biggest advantage of embedded electronic components (such as RF-MLCCs) is the significant reduction in the circuit path between this component and active components (such as ICs), thereby reducing parasitic inductance and capacitance. This is crucial for power integrity and signal integrity in high-frequency circuits, and it also saves PCB surface space, achieving greater integration.

[0052] Furthermore, this invention also provides a circuit board incorporating the aforementioned ceramic electronic components. In some embodiments, the circuit board may include other electronic components, such as integrated circuit (IC) components. In some embodiments, the circuit board may be a printed circuit board or a low-temperature co-fired ceramic circuit board. In some embodiments, the ceramic electronic components may be disposed within the circuit board (i.e., embedded) or disposed on the circuit board (e.g., adhered to the circuit board).

[0053] In some embodiments, the circuit board may include a dielectric substrate composed of a dielectric material (such as an insulating substrate composed of a dielectric material), and the ceramic electronic component is embedded in the dielectric substrate; the dielectric substrate includes a conductive pattern and a plurality of through-hole conductors, and the ceramic electronic component is connected to the conductive pattern of the dielectric substrate through the through-hole conductors. Generally, the aforementioned ceramic electronic component belongs to embedded ceramic electronic components. In some embodiments, the ceramic electronic component is embedded in the dielectric substrate by means of an electrode design.

[0054] In some embodiments, the first terminal electrode of the ceramic electronic component may be connected to the regions of the conductive patterns on the surface of the dielectric substrate via the via conductors; wherein the regions of the conductive patterns may be located on the same surface of the dielectric substrate.

[0055] Alternatively, in other embodiments, the first terminal electrode of the ceramic electronic component may be connected to the regions of the conductive patterns on the surface of the dielectric substrate via the via conductors; wherein the regions of the conductive patterns may be located on opposite surfaces of the dielectric substrate.

[0056] In other embodiments, the circuit board may further include a substrate with contact pads; the two solder layers in the ceramic electronic component are connected to the contact pads of the substrate. Generally, the aforementioned ceramic electronic component belongs to surface-mount ceramic electronic components.

[0057] Specifically, the aforementioned circuit board includes printed circuit wiring on the substrate with contact solder joints; it can stack and co-fire ceramic strips printed with metal patterns to achieve three-dimensional wiring of the circuit, and subsequently, one or more electronic components can be mounted on the substrate. Other electronic components can be connected to the solder joints in a surface mount process or fabricated in the circuit board using low temperature co-fired ceramic technology to form modules with specific functions (such as filters).

[0058] The ceramic electronic components and circuit boards created in this invention can be applied to tablet computers, smartphones, electric vehicles, in-vehicle entertainment systems, and in-vehicle driving safety assistance systems, but are not limited to these.

[0059] In the specification, the range represented by "smallest value to largest value" means, unless otherwise specified, that the range is greater than or equal to the smallest value and less than or equal to the largest value. For example, the content of the dispersant can be from 1 part by weight to 3 parts by weight, which means that the content of the dispersant is "greater than or equal to 1 part by weight and less than or equal to 3 parts by weight". Simple Explanation of the Diagram

[0060] Figure 1 is a side cross-sectional view of the first embodiment of the ceramic electronic component of this invention. Figure 2 is a side cross-sectional schematic diagram of the ceramic electronic components of Examples 1 to 44. Figure 3 is an optical microscope image of the first terminal electrode included in the ceramic electronic component of Example 3, taken in Analysis 6. Figure 4 is an optical microscope image of the first terminal electrode included in the ceramic electronic component of Comparative Example 2, taken in Analysis 6. Figures 5A to 5C are, in sequence, cross-sectional schematic diagrams of the ceramic electronic components of Examples 45 to 47, cross-sectional schematic diagrams of the ceramic body along the cut lines 5B-5B, and side end view of the ceramic body. Figure 6 is a side cross-sectional schematic diagram of the ceramic electronic components of Examples 48 to 50. Figure 7 is a side view of the first embodiment of the circuit board of this invention, wherein the ceramic electronic component is an embedded electronic component located inside the printed circuit board. Figure 8 is a side view of the second embodiment of the circuit board of this invention, wherein the ceramic electronic component is a surface-mount capacitor component connected to the substrate. Figure 9 is a side view of another embodiment of the ceramic electronic component of this invention (which can be applied to a low-temperature co-fired ceramic circuit board). Implementation

[0061] The following examples illustrate the implementation of this invention, and several comparative examples are provided for comparison. Those skilled in the art can easily understand the advantages and effects of this invention through the following examples and comparative examples. It should be understood that the examples listed in this specification are only for illustrative purposes and are not intended to limit the scope of this invention. Those skilled in the art can make various modifications and changes based on their general knowledge without departing from the spirit of this invention to implement or apply its content.

[0062] [Raw material: Composition used to form the ceramic body] [(A)] [Place] [Included glass materials]

[0063] To further confirm whether the glass material in composition (A) can form a liquid phase thin film layer on the surface of copper powder through capillary action in the subsequent process of preparing ceramic electronic components, the following analysis of the "contact angle between the glass material after sintering at 880°C and the Cu / CuaO substrate" was used to confirm the degree of affinity between these glass materials and copper and / or cuprous oxide.

[0064] I. Select one of the following six glass materials: Glass material 1: BaO-ZnO-B2O3-CaO-Al2O3-SiO2-Bi2O3-Cu2O Glass material 2: Na₂O-CaO-BaO-ZnO-B₂O₃-SiO₂-Cu₂O Glass material 3: MnO-MgO-Al2O3-SiO2-Cu2O Glass material 4: Li2O-MnO-MgO-Al2O3-SiO2-Cu2O Glass material 5: B2O3-BaO-ZnO-Al2O3-SiO2-MgO-CaO Glass material 6: SiO2-ZrO2-TiO2-Al2O3-B2O3-CaO-MgO-BaO-SrO-Li2O

[0065] First, 500 grams of each of the powdered glass materials 1 to 6 were taken and ground to a particle size D50 between 0.5 μm and 2 μm. Next, the ground glass materials were placed in a mold, and a portion of the ground glass materials was pressed into a round ingot (0.5 cm in diameter and 0.5 cm in height) using a hydraulic press (pressure 20 kg / cm²). Next, a copper substrate was prepared and heat-treated at 550°C for 1 hour in a nitrogen atmosphere (oxygen content approximately 50 ppm). This process produced a Cu₂O oxide layer on the copper substrate, resulting in a Cu / Cu₂O substrate. Then, each set of round glass materials was placed on the Cu / Cu₂O substrate as a sample of that set of glass materials. Each group of samples was placed in a sintering furnace (model: 2K25-143C77-11NC, manufacturer: Schmid), heated to 880°C and held at that temperature until the ingot-shaped glass material melted into a liquid phase to complete the sintering process; then, the contact angle between the aforementioned liquid phase glass material and the Cu / Cu2O substrate was observed and measured using a contact angle meter (model: Phoenix 150, manufacturer: Jingzhi Technology), and the results were recorded in Table 1.

[0066] In addition, each group of samples was heated to 940°C, and the contact angle between the liquid glass material and the Cu / Cu2O substrate was observed and measured using the CCD camera and contact angle meter mentioned above. The results are also recorded in Table 1.

[0067] Table 1 Serial Number Composition of glass materials Contact angle 880℃ Burning 940℃ Burning 1 BaO-ZnO-B2O3-CaO-Al2O3-SiO2-Bi2O3-Cu2O 11.3 3.8 2 Na2O-CaO-BaO-ZnO-B2O3-SiO2-Cu2O 11.5 3.7 3 MnO-MgO-Al2O3-SiO2-Cu2O 11.8 3.8 4 Li2O-MnO-MgO-Al2O3-SiO2-Cu2O 10.8 3.3 5 B2O3-BaO-ZnO-Al2O3-SiO2-MgO-CaO 28.6 22.3 6 SiO2-ZrO2-TiO2-Al2O3-B2O3-CaO-MgO-BaO-SrO-Li2O 55.5 45.3

[0068] Even though BaO-ZnO-B2O3-CaO-Al2O3-SiO2-Bi2O3-Cu2O, Na2O-CaO-BaO-ZnO-B2O3-SiO2-Cu2O, and B2O3-BaO-ZnO-Al2O3-SiO2-MgO-CaO are all glass materials that can be used in conjunction with barium titanate-based microwave dielectric oxide powder materials, the analysis results in Table 1 show that the contact angle between B2O3-BaO-ZnO-Al2O3-SiO2-MgO-CaO and the Cu / Cu2O substrate is significantly larger, indicating that its affinity with the Cu / Cu2O substrate is not high and its wettability is poor. Similarly, MnO-MgO-Al2O3-SiO2-Cu2O, Li2O-MnO-MgO-Al2O3-SiO2-Cu2O, and SiO2-ZrO2-TiO2-Al2O3-B2O3-CaO-MgO-BaO-SrO-Li2O are all glass materials that can be used in conjunction with calcium zirconate-based microwave dielectric oxide powder materials. However, as can be seen from the analysis results in Table 1, the contact angle between SiO2-ZrO2-TiO2-Al2O3-B2O3-CaO-MgO-BaO-SrO-Li2O and the Cu / Cu2O substrate is significantly larger, indicating that its affinity with the Cu / Cu2O substrate is not high and its wettability is poor. In summary, it can be inferred that in the subsequent co-firing process for preparing ceramic electronic components, selecting glass materials 1 to 4 with high affinity to the Cu / Cu2O substrate can allow these glass materials to extend to the surface of the copper powder in the composition (B) due to capillary action during the sintering process and form a liquid phase film, thereby helping to reduce the sintering temperature of the terminal electrode containing it and making it sinter dense.

[0069] [Preparation Example] [A1] [To the preparation example] [A30] [Composition] [(A)]

[0070] First, according to Table 2-1, in Preparation Examples A1 to A30, specific main powder materials and / or dopants, as well as specific glass materials, were added to an organic solvent (a mixed solution of toluene and ethanol, with a weight ratio of 1:1) in specific proportions and mixed. Next, a dispersant (manufacturer: BYK, model: DISPERBYK-2001) was added to the organic solvent to form a first mixture. Subsequently, after grinding and dispersing the first mixture, a binder (polyvinyl butyral resin) and a plasticizer (DEHP) were added and thoroughly stirred to form a ceramic slurry. Then, each group used a coating molding method to produce multiple ceramic strips with a thickness of 0.22 mm. Wherein, based on the total weight of the composition (A), the content of the organic solvent is 34±0.5 wt%, the content of the dispersant is 2.0±0.15 wt%, the content of the binder is 6±0.5 wt%, the content of the plasticizer is 3±0.5 wt%, and the remaining weight (55±0.5 wt%) is the sum of the weights of the main powder material, the dopant (if any), and the glass material.

[0071] To further clarify, the "amount of main powder material" recorded in Table 2-1 is defined as the weight percentage of "(main powder material) / (main powder material + dopant + glass material)"; the "amount of dopant" is defined as the molar percentage of "(dopant) / (main powder material)"; and the "amount of glass material" is defined as the weight percentage of "(glass material) / (main powder material + dopant + glass material)".

[0072] Since the loss of the ceramic layer itself is also one of the important factors affecting the overall signal transmission loss of ceramic electronic components, preparation examples A1 to A30 first used simplified ceramic layer simulation samples to confirm the correlation between the type of ceramic material and signal propagation loss.

[0073] Each group of simulated samples was prepared as follows: approximately 20±5 pieces of the ceramic strip were stacked on top of each other and subjected to a pressure equalization step, and then cut into a round ingot blank; subsequently, a copper inner electrode layer composition was coated on the upper and lower surfaces of the round ingot blank, and then a desizing step and a sintering step were performed in sequence. Finally, a round ingot-shaped simulated sample with a diameter of 10±1.5 mm and a thickness of 5±0.5 mm was obtained. The copper internal electrode layer composition (a) used in the simulated samples of preparation examples A1 to A19 comprises: 52.0 wt% copper powder (D50 of 0.5 μm to 1 μm), 3.0 wt% ceramic powder (BaTi4O9, with D50 of 0.1 μm to 0.2 μm), 1.5 ± 0.25 wt% ethyl cellulose resin, and 43.5 ± 3 wt% terpineol solvent; the copper internal electrode layer composition (b) used in the simulated samples of preparation examples A20 to A29 comprises: 52.0 wt% copper powder (D50 of 0.5 μm to 1 μm), 3.0 wt% ceramic powder (CaZrO3, with D50 of 0.1 μm to 0.2 μm), 1.5 ± 0.25 wt% ethyl cellulose resin, and 43.5 ± 3 wt% terpineol solvent.

[0074] The desizing step includes heating to 300°C to 550°C using a slow heating method (heating rate of 0.5°C / min to 1°C / min), holding at this temperature for a specific time, and then cooling to 40°C. The total time for the desizing step is approximately 24 to 36 hours (including overall heating, high-temperature holding, and cooling). Additionally, the sintering is carried out in a sintering atmosphere at a specific sintering temperature for 1 to 3 hours. The specific sintering temperatures and sintering atmospheres used in each group are recorded in Table 2-2, where the gas content ratio of the sintering atmosphere is expressed as a volume percentage (vol%).

[0075] Table 2-1 Preparation Example No. Main powder material dopant glass materials type Dosage type Dosage type Dosage A1 BaTi4O9 90 -- 0 Glass Material 1 10 A2 90 Glass material 2 10 A3 95 Glass Material 1 5 A4 85 Glass Material 1 15 A5 80 Glass Material 1 20 A6 BaTi4O9 90 MnCO3 0.55 ±0.08 Glass Material 1 10 A7 90 Glass material 2 10 A8 BaTi4O9 90 CaCO3 5.5 ±0.5 Glass Material 1 10 A9 90 Glass material 2 10 A10 BaTi4O9 90 SrCO3 2.5 ±0.1 Glass Material 1 10 A11 90 Glass material 2 10 A12 BaTi4O9 90 ZrO2 6.5 ±0.15 Glass Material 1 10 A13 90 Glass material 2 10 A14 BaTi4O9 90 Dy2O3 1 ±0.2 Glass Material 1 10 A15 90 Glass material 2 10 A16 BaTi4O9 90 BaWO4 2 ±0.2 Glass Material 1 10 A17 90 Glass material 2 10 A18 Ba2Ti9O20 90 -- 0 Glass Material 1 10 A19 90 Glass material 2 10 A20 CaZrO3 90 -- 0 Glass material 3 10 A21 90 Glass material 4 10 A22 95 Glass material 4 5 A23 85 Glass material 4 15 A24 Ca(Zr0.9Mn0.1)O3 90 -- 0 Glass material 3 10 A25 90 Glass material 4 10 A26 (Ca0.9Sr0.1)(Zr0.9Mn0.1)O3 90 -- 0 Glass material 3 10 A27 90 Glass material 4 10 A28 (Ca0.9Sr0.1)(Zr0.8Mn0.2)O3 90 -- 0 Glass material 3 10 A29 90 Glass material 4 10 A30 BaTi4O9 90 -- 0 Glass material 5 10

[0076] [analyze] [1] Dielectric properties of the simulated sample [ ]

[0077] A capacitance meter (manufacturer: Agilent Technologies, Inc., model: 4278A) was used to measure the capacitance of simulated samples A1 to A29 under a 1 MHz AC signal and an applied bias voltage of 1 Vrms. The dielectric constant (εr) of the ceramic material contained in each sample was calculated, and the dielectric loss (tanδ) and quality factor (Q) of the ceramic material contained in each sample were measured under the same conditions. Q was defined as 1 / (tanδ). The number of samples measured in each group (sample size, SS) was 100, and the average value was recorded in Table 2-2.

[0078] Wherein, if the tanδ measured by the simulated sample is less than 6*10-4, it indicates that its dielectric loss is low and can be defined as "good"; if the tanδ measured by the simulated sample is between 6*10-4 and 1*10-3, it indicates that its dielectric loss is moderate and is defined as "acceptable"; if the tanδ measured by the simulated sample is greater than 1*10-3, it indicates that its dielectric loss is high and is defined as "poor".

[0079] [analyze] [2] [Insulation resistance of the simulated sample]

[0080] [ ] A high resistance meter (manufacturer: Keysight Technology Co., Ltd., model: Keysight 4339B) was used to analyze the simulated samples prepared in Examples A1 to A29. A voltage of 100 V was applied for 5 seconds to each sample, and its leakage current was measured. The insulation resistance was obtained by dividing the voltage by the leakage current, and the results were recorded in Table 2-2. The number of measurements for each group of samples was 100, and the average value and standard deviation were calculated.

[0081] If the insulation resistance measured by the simulated sample is greater than 1*10¹¹ Ω, it indicates that it can avoid leakage between the component and the external contact or between the internal electrode and the terminal electrode. Therefore, its current carrying capacity can be rated as "good".

[0082] [analyze] [3] [Temperature capacitance coefficient of the simulated sample]

[0083] As previously mentioned, a capacitance meter (manufacturer: Agilent Technologies, Inc., model: 4278A) was used to measure the capacitance of simulated samples A1 to A29 under a 1 MHz AC signal and an applied bias voltage of 1 Vrms. However, the simulated samples were placed in a variable temperature chamber with controllable temperature, and the capacitance change from -55°C to 125°C was measured. The temperature capacitance coefficient of each simulated sample was calculated using the formula: "Temperature capacitance coefficient = {(CT – C25) / [C25×(T– 25)]}×106 ppm / °C". In the above formula for calculating the temperature capacitance coefficient, the temperature capacitance coefficient change is defined relative to room temperature (25°C), T is the test temperature (-55°C or 125°C), CT is the static capacitance of the simulated sample at the test temperature (-55°C or 125°C), and C25 is the static capacitance at 25°C.

[0084] Among them, the temperature capacitance coefficients of the simulated samples prepared in Examples A1 to A29 are all classified as NP0 (±30 ppm / °C), which means that their capacitance is very stable in the operating range of -55°C to 125°C with minimal capacitance variation.

[0085] Table 2-2 Preparation Example serial number Sintering temperature (°C) sintering atmosphere Dielectric constant Q @1 MHz insulation resistance (Ω) Dielectric loss tan δ @1 MHz A1 950±20 N2 35.81 4245 7.15*10¹² 2.36*10-4 A2 950±20 35.78 4247 8.17*10¹² 2.35*10-4 A3 960±20 36.52 3666 5.43*1011 2.73*10-4 A4 950±20 33.12 3808 2.85*1012 2.63*10-4 A5 940±20 31.67 2910 3.95*1012 3.44*10-4 A6 950±20 35.45 4986 7.96*1012 2.01*10-4 A7 950±20 35.13 4988 7.47*1012 2.00*10-4 A8 950±20 33.53 5671 6.90*1012 1.76*10-4 A9 950±20 33.85 5704 7.40*1012 1.75*10-4 A10 950±20 34.63 5753 5.89*1012 1.74*10-4 A11 950±20 34.87 5702 5.04*1012 1.75*10-4 A12 950±20 35.87 4571 8.79*1012 2.19*10-4 A13 950±20 35.71 4604 7.45*1012 2.17*10-4 A14 950±20 36.28 5971 5.97*1012 1.67*10-4 A15 950±20 35.79 5908 6.45*1012 1.69*10-4 A16 950±20 33.66 5588 8.97*1012 1.79*10-4 A17 950±20 33.72 5904 6.43*1012 1.69*10-4 A18 950±20 37.33 5171 7.59*1012 1.93*10-4 A19 950±20 37.21 5004 6.48*1012 2.00*10-4 A20 950±20 99 vol% N2 + 1 vol% H2 28.75 4573 7.90*1012 2.19*10-4 A21 950±20 28.81 4578 8.40*1012 2.18*10-4 A22 960±20 25.61 3123 4.90*1011 3.20*10-4 A23 950±20 25.85 2457 5.30*1012 4.07*10-4 A24 950±20 27.76 4753 7.90*1012 2.10*10-4 A25 950±20 27.87 4708 8.40*1012 2.12*10-4 A26 950±20 26.75 4873 7.69*1012 2.05*10-4 A27 950±20 26.81 4988 8.74*10¹² 2.00*10-4 A28 950±20 28.75 4793 7.39*10¹² 2.09*10-4 A29 950±20 28.84 4898 8.74*10¹² 2.04*10-4

[0086] [Preparation Example] [A1-2] [To the preparation example] [A30-2] [Composition] [(A)]

[0087] According to the proportions shown in Table 2-3, ceramic slurries were prepared for use in the following examples A1-2 to A30-2 (i.e., the formulations for preparing the ceramic body) of ceramic electronic components. The preparation methods and ceramic slurries used in examples A1-2 to A30-2 are similar to those used in the compositions (A) of examples A1 to A30, with the only difference being the content of each component.

[0088] Table 2-3 Preparation Example No. Main powder Material Glass Material Main powder materials and glass materials dispersant solvent plasticizers adhesive type serial number weight ratio sum (wt%) content (wt%) content (wt%) content (wt%) content (wt%) A1-2 BaTi4O9 Glass Material 1 9:1 54.01 1.60 34.92 3.05 6.42 A2-2 Glass Material 2 53.50 1.77 35.50 3.25 5.98 A3-2 BaTi4O9 Glass Material 1 9.5:0.5 54.01 1.60 34.92 3.05 6.42 A4-2 8.5:1.5 54.01 1.60 34.92 3.05 6.42 A5-2 8:2 54.01 1.60 34.92 3.05 6.42 A6-2 BaTi4O9 + 0.55 mole% MnCO3 Glass Material 1 9:1 52.50 1.78 36.50 3.33 5.89 A7-2 Glass Material 2 54.50 1.80 34.60 3.08 6.02 A9-2 BaTi4O9 + 5.5 mole% CaCO3 Glass Material 2 9:1 56.30 1.25 32.50 2.85 7.10 A10-2 BaTi4O9 + 2.5 mole% SrCO3 Glass Material 1 9:1 56.30 1.25 32.50 2.85 7.10 A12-2 BaTi4O9 + 6.5 mole% ZrO2 Glass Material 1 9:1 56.30 1.25 32.50 2.85 7.10 A13-2 Glass Material 2 56.30 1.25 32.50 2.85 7.10 A14-2 BaTi4O9 + 1.0 mole% Dy2O3 Glass Material 1 9:1 56.30 1.25 32.50 2.85 7.10 A15-2 Glass Material 2 56.30 1.25 32.50 2.85 7.10 A16-2 BaTi4O9 + 2.0 mole% BaWO4 Glass Material 1 9:1 56.30 1.25 32.50 2.85 7.10 A17-2 Glass Material 2 56.30 1.25 32.50 2.85 7.10 A19-2 Ba2Ti9O20 Glass Material 2 9:1 56.30 1.25 32.50 2.85 7.10 A20-2 CaZrO3 Glass Material 3 9:1 50.30 1.25 38.60 3.05 6.80 A21-2 Glass Material 4 50.30 1.25 38.60 3.05 6.80 A24-2 Ca- (Zr0.9Mn0.1)O3 Glass Material 3 9:1 50.30 1.25 38.60 3.05 6.80 A25-2 Glass Material 4 50.30 1.25 38.60 3.05 6.80 A26-2 (Ca0.9Sr0.1)- (Zr0.9Mn0.1)O3 Glass Material 3 9:1 50.30 1.25 38.60 3.05 6.80 A27-2 Glass Material 4 50.30 1.25 38.60 3.05 6.80 A28-2 (Ca0.9Sr0.1)- (Zr0.8Mn0.2)O3 Glass Material 3 9:1 50.30 1.25 38.60 3.05 6.80 A29-2 Glass Material 4 50.30 1.25 38.60 3.05 6.80 A30-2 BaTi4O9 Glass Material 5 9:1 54.01 1.60 34.92 3.05 6.42

[0089] [Preparation Example] [B1] [To the preparation example] [B6] [Composition] [(B)]

[0090] First, the mixtures were prepared according to the proportions shown in Table 3, and then dispersed evenly using a three-roller to obtain compositions (B) (i.e., copper-containing first-end electrode pastes) for Preparation Examples B1 to B6. In Preparation Examples B1 to B6, the "copper powder" consisted of copper powder A with an average particle size (D50) of 0.5 μm to 5 μm and copper powder B with an average particle size (D50) of 6 μm to 10 μm, with a ratio of copper powder A to copper powder B of 3:7. The "resin" in Preparation Examples B1 to B6 was a methyl methacrylate resin (manufacturer: Kusumoto, model: ER2300). The "electrode paste solvent" in Preparation Examples B1 to B6 was terpineol (manufacturer: Yasuhara Chemical Co., Ltd., model: Terpineol). The "glass material" in Preparation Example B6 was B2O3-BaO-ZnO-SiO2-Al2O3-Na2O. In other embodiments, composition (B) may also contain dispersants and leveling agents to further smooth its appearance and coating during subsequent adhesion steps, without the formation of sharp or concave ends.

[0091] To further clarify, the amounts of “copper powder,” “resin,” “electrode paste solvent,” and “glass material” recorded in Table 3 are all defined relative to the “total weight of composition (B).”

[0092] [analyze] [4] Embryo density

[0093] In this analysis, compositions (B) of preparation examples B1 to B6 were coated into films at a rate of 10 mm / s, resulting in films with a thickness of approximately 300 μm. These films were then dried at 120°C for 20 minutes. After drying, the films were cut into rectangular samples with dimensions of 1 cm in length and width. The film thickness and calculated volume (V) were then measured using calipers. The green density of each group of samples was calculated using the formula: green density (D) = weight / V. Five samples were measured in each group, and their average values ​​are recorded in Table 3.

[0094] Table 3 Preparation Example serial number Copper powder (wt%) resin (wt%) Electrode paste Solvent (wt%) glass materials (wt%) Copper powder / resin weight ratio Embryo density (g / cm3) B1 75 3.9 21.1 0 19.23 5.15 B2 75 4.0 21.0 0 18.65 5.05 B3 75 7.0 18.0 0 10.72 4.65 B4 75 8.4 16.6 0 8.93 4.00 B5 75 9.0 16.0 0 8.33 3.86 B6 75 7.0 13.0 5 10.72 4.38

[0095] Please refer to Figure 1. The ceramic electronic component 1 of this invention includes a ceramic body 10 and two first end electrodes 20. The ceramic body 10 has a first end face 101 and a second end face 102 facing each other. Furthermore, the ceramic body 10 includes a plurality of ceramic sublayers 11 and a plurality of inner electrodes 12. The ceramic sublayers 11 and the inner electrodes 12 are alternately stacked within the ceramic body 10. Two adjacent inner electrodes 12 are respectively connected to the first end face 101 and the second end face 102 of the ceramic body 10. The two first end electrodes 20 respectively cover the first end face 101 and the second end face 102 of the ceramic body 10 and are electrically connected to the inner electrodes 12. Although the number of inner electrode layers 12 shown in Figure 1 is 5, the number of ceramic sublayers 11 and inner electrodes 12 in the figure is mainly for illustrative purposes and is not intended to limit the ceramic electronic component of this invention.

[0096] [Example] [1] [To the Example] [36(E1)] [to] [E36)] [Ceramic Electronic Components] [(] [Surface Adhesive] [RF-MLCC]

[0097] First, according to Table 4-1, each embodiment further prepares a ceramic body from the ceramic ribbon formed by the composition (A) of the specific preparation example obtained according to Table 2-3: multiple identical ceramic ribbons with a specific thickness (approximately 15 μm) are prepared by coating molding method (i.e., after subsequent sintering, they are distinguished into a ceramic top layer, a ceramic sublayer, and a ceramic bottom layer according to their position in the ceramic body). Next, the copper internal electrode layer composition is coated onto the upper surface of a portion of the ceramic ribbons by screen printing method. The remaining ceramic ribbons without the aforementioned copper internal electrode layer composition are referred to as blank ceramic ribbons. Then, in a stacking device, some blank ceramic ribbons are placed at the bottom (for forming the ceramic bottom layer); then, ceramic ribbons coated with the copper internal electrode layer composition are stacked sequentially (the electrode layer compositions are all facing upwards); finally, some blank ceramic ribbons are placed at the top (for forming the ceramic top layer) to form a stacked structure. The copper inner electrode layer composition used in Examples 1 to 28 is the aforementioned copper inner electrode layer composition (a); the copper inner electrode layer composition used in Examples 29 to 36 is the aforementioned copper inner electrode layer composition (b).

[0098] Next, the aforementioned stacked structure is subjected to a pressure equalization step and a cutting step to form a green body. Then, the green body undergoes a debinding step and a sintering step in sequence to obtain a sintered ceramic body (also known as a cooked body). The aforementioned debinding step includes heating to 500±10°C at a slow rate (0.5°C / min to 1°C / min), holding at this temperature for 4 hours, and then cooling to 40°C; the total time of the debinding step (BBO) is approximately 48 hours (including overall heating, high-temperature holding, and cooling); the aforementioned sintering step includes sintering at a nitrogen atmosphere (oxygen content of 1 ppm) at a temperature of 950±20°C, and holding at the aforementioned sintering temperature for 2 hours; the sintering step includes heating to 920±20°C at a slow rate (15°C / min to 30°C / min), holding at this temperature for 15 minutes, and then cooling to room temperature.

[0099] Next, the acute angle of the sintered ceramic body is removed to facilitate the coverage of the corners of the subsequent end electrodes. Then, according to Table 4-1, the first end electrode paste formed by the composition (B) of the specific preparation example prepared according to Table 3 is impregnated onto the opposite two end faces of the sintered body of the ceramic body, and then a curing step is performed under a protective atmosphere; wherein, the curing step first goes through a desizing stage (at a temperature of 650°C for 30 minutes under a nitrogen atmosphere with an oxygen content of less than 1 ppm), followed by a sintering stage (at a maximum temperature of 920°C for 30 minutes under a nitrogen atmosphere with an oxygen content of less than 0.1 ppm), to form the two first end electrodes on the opposite two end faces (i.e., the first end face and the second end face) of the sintered body of the ceramic body; then, a nickel metal layer is plated on the outside of the first end electrode as the second end electrode (average thickness of about 3 μm); then, a tin metal layer is plated on the outside of the second end electrode as a flux layer (average thickness of 8 μm), and finally the ceramic electronic components of each embodiment are obtained. The dimensions of the ceramic electronic components are as follows: length 1.6 ± 0.2 mm. × Width 0.8±0.2 mm × Thickness 0.8±0.2 mm. The end electrode obtained through the sintering step not only has a dense structure to prevent moisture intrusion, but also allows for better bonding with the internal electrodes within the ceramic body. Furthermore, in some embodiments, the thickness of the ceramic electronic component can be achieved primarily by adjusting the thickness of the ceramic top cover layer and / or the ceramic bottom cover layer (e.g., the number of layers of blank ceramic strip); or, it can also be achieved by adjusting the thickness of the internal electrodes. To further explain, the ceramic electronic components of Examples 1 to 36 have their respective ceramic top cover layer and ceramic bottom cover layer thicknesses adjusted according to the target capacitance value and the number and thickness of the aforementioned ceramic sublayers and internal electrodes. To make subsequent ESR measurements more accurate, the screening capacitance (in picofarads (pF)) of the samples of Examples 1 to 36 was set to 5.6±0.02 pF (1 pF=1*10-12 F) at 1 MHz, and the actual screening capacitance values ​​for each group are recorded in Table 4-2.

[0100] Referring to Figure 2, the ceramic electronic component 1 of Embodiments 1 to 36 includes a ceramic body 10 and two first end electrodes 20; wherein the ceramic body 10 has a first end face 101 and a second end face 102 opposite to each other. Furthermore, the ceramic body 10 includes a plurality of ceramic sublayers 11 and a plurality of inner electrodes 12; wherein the ceramic sublayers 11 and the inner electrodes 12 are alternately stacked within the ceramic body 10; in addition, the ceramic body 10 also includes a ceramic upper cover layer 13 and a ceramic lower cover layer 14, which sandwich the stacked layers of ceramic sublayers 11 and inner electrodes 12 therein. Two adjacent inner electrodes 12 are respectively connected to the first end face 101 and the second end face 102 of the ceramic body 10; the two first end electrodes 20 respectively cover the first end face 101 and the second end face 102 of the ceramic body 10 and are electrically connected to the inner electrodes 12. Furthermore, the ceramic electronic component 1 also includes two second terminal electrodes 30 and two flux layers 40; the two second terminal electrodes 30 are respectively formed on the outer surfaces of the two first terminal electrodes 20, and the two flux layers 40 are respectively formed on the outer surfaces of the two second terminal electrodes 30; that is, the first end face 101 and the second end face 102 of the ceramic body 10 are sequentially covered by the first terminal electrode 20, the second terminal electrode 30 and the flux layer 40 from the inside out. Similarly, although the number of inner electrode layers 12 shown in FIG2 is 5, the number of ceramic sublayers 11 and inner electrodes 12 in the figure is mainly for illustrative purposes and is not the actual number contained in the aforementioned ceramic electronic component.

[0101] [Comparative Example] [1] [to] [22(C1)] [to] [C22)] [:] [Ceramic Electronic Components] [(] Surface-mount RF multilayer ceramic capacitor [)]

[0102] The methods used to prepare the comparative examples are similar to those used to prepare the ceramic electronic components of Examples 1 to 36. The main differences are: the composition (A) used to form the ceramic body and / or the composition (B) used to form the first terminal electrode are different. The raw materials used in each comparative example are shown in Table 4-1. In addition, the copper inner electrode layer composition used in Comparative Examples 1 to 14 is the aforementioned copper inner electrode layer composition (a); the copper inner electrode layer composition used in Comparative Examples 15 to 22 is the aforementioned copper inner electrode layer composition (b).

[0103] [analyze] [5] [:Prep formation properties of the first end electrode]

[0104] In this analysis, an optical microscope (model: BX60, manufacturer: Olympus) was used to observe and confirm the surface appearance of the green embryo of the first end electrode formed after coating the composition (B) during the preparation process of each example and comparative example. If the proportion of samples with surface sagging, uneven thickness, end electrode damage, or pointed tip phenomenon of the green embryo of the first end electrode is greater than 5% of the total number of samples measured, it is rated as "poor"; if the proportion of samples with the above conditions is less than 5% but greater than 0.1% of the total number of samples measured, it is rated as "fair"; if none of the above conditions are present, it is judged as "good"; the total number of samples measured in this analysis is 100. The above analysis results are recorded in Table 4-1.

[0105] [analyze] [6] [Percentage of glass in the first electrode]

[0106] In this analysis, an optical microscope (model: BX60M, manufacturer: Olympus) and Image Pro-10 imaging software were used to observe and analyze the glass content in the first end electrode formed by the composition (B) in each embodiment and comparative example, and the above analytical results are recorded in Table 4-1. Furthermore, please refer to Figure 3, with the figure of Example 3 representing each embodiment; on the other hand, please refer to Figure 4, with the figure of Comparative Example 2 representing each comparative example.

[0107] [analyze] [7] [Compactness of the first electrode]

[0108] The density of the first terminal electrode in each ceramic electronic component of the embodiments and comparative examples was evaluated by fluorescence penetrant destructive physical analysis, and the evaluation results are listed in Table 4-1. Specifically, a fluorescence-observable microscope (model: BX61, manufacturer: Olympus) and image software Image Pro-10 were used to analyze the fluorescence penetrant area to obtain the fluorescence permeability; if the fluorescence permeability of the cross-section of the first terminal electrode was 0%, its density was judged to be "good"; if the fluorescence permeability of the cross-section of the first terminal electrode was greater than 0% and less than or equal to 3%, its density was judged to be "fair"; if the fluorescence permeability of the cross-section of the first terminal electrode was greater than 3%, its density was judged to be "poor".

[0109] [analyze] [8] [Interface morphology between the first terminal electrode and the ceramic body]

[0110] In this analysis, the ceramic electronic components of each embodiment and comparative example were observed using a secondary electron microscope (SEM) to check for glass bubbling, and destructive analysis was performed to observe the interface of the first terminal electrode to confirm whether bubbles existed at the interface between the first terminal electrode and the ceramic body. The observation results are recorded below: 1-1. No glass floating phenomenon was found in the first terminal electrode of the ceramic electronic components in Examples 1 to 36; 1-2. In Comparative Examples 1, 3 to 22, the first terminal electrode of the ceramic electronic components all exhibited glass floating phenomenon; 1-3. No glass floating phenomenon was found at the first terminal electrode of the ceramic electronic component in Comparative Example 2. 2-1. No bubbles were found at the interface between the first terminal electrode and the ceramic body of the ceramic electronic components in Examples 1 to 36; 2-2. Bubbles were found at the interface between the first terminal electrode and the ceramic body of the ceramic electronic components in Comparative Examples 1, 3 to 22; 2-3. No bubbles were found at the interface between the first terminal electrode and the ceramic body of the ceramic electronic component in Comparative Example 2.

[0111] [analyze] [9] [Resistivity of the first electrode]

[0112] In the manufacturing process of ceramic electronic components in Examples 1 to 36 and Comparative Examples 1 to 22, after the first terminal electrode was formed by composition (B), the resistivity of the first terminal electrode was measured using a four-point probe instrument (model PII-QT5601Y). The number of samples measured in each group was 10, and the average value was recorded in Table 4-1.

[0113] If the measured resistivity is less than or equal to 5×10⁻⁷ Ω·m, its resistance performance is judged to be "good"; conversely, if the measured resistivity is greater than 5×10⁻⁷ Ω·m, its resistance performance is judged to be "poor".

[0114] [analyze]

[10] [:weldability]

[0115] Solderability testing involves first printing solder paste onto a test PCB, then soldering each group of ceramic electronic components onto the PCB using surface mount technology (STM) (sample size: 1000 components). The test observes for solder spraying, tombstoning, and exposed copper (area less than 5% is considered failure). If any of these defects are found, the solderability is deemed "poor"; otherwise, if none are detected, the solderability is deemed "good". The evaluation results are listed in Table 4-1.

[0116] [analyze]

[11] [:Joint strength of flux layer] [ / ] [Extreme Tension]

[0117] On the two flux layers at opposite ends of the ceramic electronic components of Examples 1 to 36 and Comparative Examples 1 to 22, iron wires were soldered onto each other with lead-free solder paste. The iron wires were then clamped with a universal stretching machine (model: 204, manufacturer: Rundai Precision Machinery Industrial Co., Ltd.) and stretched in opposite directions. The ultimate tensile force was measured. The number of samples measured in each group was 10, and the average value was recorded in Table 4-1.

[0118] If the measured ultimate tensile force is greater than 2 kgf, the bond strength is judged as "good"; if the measured ultimate tensile force is greater than or equal to 1.5 kgf and less than or equal to 2 kgf, the bond strength is judged as "medium"; if the measured ultimate tensile force is less than 1.5 kgf, the bond strength is judged as "poor".

[0119] [analyze]

[12] [Unscreened resistor tolerance] [(COV, R , %)] [Tolerances for unscreened capacitors] [(COV, C , %)]

[0120] Unselected capacitance tolerance (COVC%) is an important indicator for evaluating the accuracy of copper-containing terminal electrodes in high-quality RF-MLCCs, while both COVC% and unselected resistance tolerance (COVR%) are indicators for evaluating the stability of the resistance process. First, the DC resistance values ​​(hereinafter referred to as "resistance") of ceramic electronic components in Examples 1 to 36 and Comparative Examples 1 to 22 were measured according to JIS C 5201-1:Clause 4.5 using a four-wire resistance measurement system (manufacturer: Bankala Technology, model: RM3543). Furthermore, the COVR% of each group was calculated using the formula "Unselected resistance tolerance (COVR%) = Resistance standard deviation / Resistance average value". During testing, 100 samples were measured in each group, and the average value was recorded. The COVC% of each group was calculated according to the formula "Unscreened Capacitance Tolerance (COVC%) = Capacitance Standard Deviation / Capacitance Average Value". The number of samples measured in each group was 100. The average value of COVC was recorded in Table 4-2. The COVC of subsequent specific embodiments and comparative examples was recorded in Table 8-2.

[0121] If the obtained COVR or COVC is less than or equal to 3%, it is judged to have good electrical stability; conversely, if the obtained COVR or COVC is greater than 3%, it is judged to have poor electrical stability.

[0122] [analyze]

[13] Dielectric loss [ tan δ ( ] [exist] [1 MHz] [Below the frequency] [) ]

[0123] The dielectric loss (tanδ) of the ceramic electronic components of Examples 1 to 36 and Comparative Examples 1 to 22 was measured in the same manner as described in Analysis 1 above. For each group of samples, 100 samples were measured, and the average value was recorded in Table 4-2.

[0124] Wherein, if the tanδ measured by the simulated sample is less than 5*10-4, it indicates that its dielectric loss is low and can be defined as "good"; if the tanδ measured by the simulated sample is greater than or equal to 5*10-4, it indicates that its dielectric loss is high and is defined as "bad".

[0125] [analyze]

[14] [Insulation resistance]

[0126] The ceramic electronic components of Examples 1 to 36 and Comparative Examples 1 to 22 were analyzed using a high resistance meter (manufacturer: Keysight Technology Co., Ltd., model: Keysight 4339B). A voltage of 100 V was applied for 5 seconds to each sample, and its leakage current was measured. The insulation resistance was obtained by dividing the voltage by the leakage current. The number of samples measured in each group was 100, and the average value was recorded in Table 4-2.

[0127] [analyze]

[15] [Equivalent series resistance] [(ESR)] [With quality factors] [(Q)]

[0128] In this analysis, an impedance analyzer (manufacturer: Keysight Technology Co., Ltd., model: Keysight E4991B) was used to measure the equivalent series resistance and quality factor of ceramic electronic components in Examples 1 to 36 and Comparative Examples 1 to 22 at 1 GHz; the number of samples measured was 5, and the average value was recorded in Table 4-2.

[0129] [analyze]

[16] [Water vapor intrusion failure test]

[0130] [(I)] [Capacitor Component Moisture Intrusion Failure Test:]

[0131] According to the IEC 60068 standard for moisture intrusion failure testing, ceramic electronic components (capacitors) of Examples 1 to 44 (E1~E44) and Comparative Examples 1 to 26 (C1~C26) were placed in a constant temperature and humidity chamber (manufacturer: Hitachi, model: EC-86MHHPE). The temperature of the constant temperature and humidity chamber was 40±2°C, the relative humidity was 90% to 95%, the test time was 500+24 / -0 hours, and a rated voltage of 100 V was applied to each group of samples. The appearance of each group of samples was observed to see if there was any obvious damage. Next, the electrical characteristics of the sample were used to determine whether moisture intrusion caused the ceramic electronic components to fail: (1) the capacitance change rate was less than ±0.5 pF, (2) the quality factor (Q) was greater than or equal to 100+10 C (where C is the capacitance value), and (3) the insulation resistance was greater than or equal to 1*109 Ω. If all three electrical characteristics conditions were met, the sample was deemed "qualified". If the sample did not meet one or more of the electrical characteristics conditions, it was deemed "failed". In each group, 100 identical ceramic electronic components were measured, and the "proportion of the number of failures to the total" was used as the moisture intrusion failure rate.

[0132] If the obtained water vapor intrusion failure rate is 0%, its reliability is rated as "good"; if the obtained water vapor intrusion failure rate is greater than 0% and less than 15%, its reliability is rated as "fair"; if the obtained short-term instantaneous load failure rate is greater than or equal to 15%, its reliability is rated as "poor". The evaluation results are listed in Table 4-2.

[0133] [(II)] [Connector component moisture intrusion failure test:]

[0134] The moisture intrusion failure test was conducted according to JIS C 5201-1:Clause 4.24. First, the ceramic electronic components (multilayer connector electronic components) of Examples 45 to 53 (E45~E53) and Comparative Examples 27 to 29 (C27~C29) were placed in a constant temperature and humidity chamber (manufacturer: Hitachi, model: EC-86MHHPE) for 1000 hours; wherein the temperature of the constant temperature and humidity chamber was 40±2°C and the relative humidity was 90% to 95%. Next, a power supply (manufacturer: Keysight Technologies Co., Ltd., model: E3640A) was used to apply a 0.5 amp current to each group of samples in a switching cycle (1.5 hours on, 0.5 hours off), and the presence of open circuits or resistance exceeding 50 mΩ was observed. If any of these conditions were observed, the sample was considered "failed." For each group, 100 identical connector electronic components were measured, and the failure rate was defined as the percentage of failures out of the total. A 0% water vapor intrusion failure rate was rated as "good"; a failure rate greater than 0% and less than or equal to 30% was rated as "fair"; and a failure rate greater than 30% was rated as "poor." The evaluation results are listed in Table 4-2.

[0135] Table 4-1 Example / Comparative Example Number Preparation example number of composition (A) Preparation example number of composition (B) First terminal electrode Bond strength of flux layer (Kgf) Embryo formation Total glass area percentage (%) density resistivity (10⁻⁷ Ω·m) weldability E1 A1-2 B1 acceptable 0.12 good 1.32 good 2.34 E2 B2 good 0.15 good 1.36 good 2.45 E3 B3 good 0.13 good 1.28 good 2.27 E4 B4 good 0.10 good 2.94 good 1.94 E5 B5 good 0.10 good 3.14 good 1.53 C1 B6 good 22.76 Difference 65.4 inferior 1.10 C2 A30-2 B3 good 0.11 Difference 75.6 inferior 0.90 E6 A2-2 B1 acceptable 0.11 good 1.22 good 2.35 E7 B2 good 0.16 good 1.25 good 2.55 E8 B3 good 0.14 good 1.18 good 2.35 E9 B4 good 0.13 good 2.54 good 2.03 E10 B5 good 0.12 good 3.15 good 1.56 C3 B6 good 23.2 Difference 75.4 inferior 1.18 E11 A6-2 B1 acceptable 0.12 good 1.10 good 2.33 E12 B2 good 0.14 good 1.22 good 2.51 E13 B3 good 0.13 good 1.28 good 2.45 E14 B4 good 0.15 good 2.56 good 2.12 E15 B5 good 0.13 good 3.56 good 1.67 C4 B6 good 22.6 Difference 69.3 inferior 1.23 E16 A7-2 B1 acceptable 0.13 good 1.12 good 2.26 E17 B2 good 0.14 good 1.20 good 2.68 E18 B3 good 0.13 good 1.25 good 2.42 E19 B4 good 0.10 good 2.44 good 2.13 C5 B6 good 23.2 Difference 67.8 inferior 1.10 E20 A9-2 B3 good 0.14 good 1.36 good 2.45 C6 B6 good 22.52 good 53.6 inferior 1.00 E21 A10-2 B3 good 0.14 good 1.28 good 2.27 C7 B6 good 23.04 good 53.6 inferior 1.36 E22 A12-2 B3 good 0.13 good 3.14 good 2.31 E23 A13-2 good 0.16 good 3.18 good 2.28 C8 A12-2 B6 good 22.60 good 59.8 inferior 1.42 C9 A13-2 good 22.76 good 59.8 inferior 1.26 E24 A14-2 B3 good 0.15 good 3.20 good 2.37 E25 A15-2 good 0.13 good 3.33 good 2.33 C10 A14-2 B6 good 22.56 good 61.2 inferior 1.15 C11 A15-2 good 22.88 good 57.8 inferior 1.19 E26 A16-2 B3 good 0.13 good 3.15 good 2.24 E27 A17-2 good 0.13 good 3.29 good 2.26 C12 A16-2 B6 good 23.08 good 58.8 inferior 1.11 C13 A17-2 good 22.20 good 51.4 inferior 1.08 E28 A19-2 B3 good 0.15 good 3.57 good 2.35 C14 B6 good 22.12 good 53.8 inferior 1.13 E29 A20-2 B3 good 0.14 good 1.26 good 2.25 E30 A21-2 good 0.13 good 1.24 good 2.28 C15 A20-2 B6 good 22.60 good 56.6 inferior 1.23 C16 A21-2 good 22.64 good 54.4 inferior 1.12 E31 A24-2 B3 good 0.13 good 1.24 good 2.25 E32 A25-2 good 0.14 good 1.21 good 2.22 C17 A24-2 B6 good 21.80 good 53.6 inferior 1.25 C18 A25-2 good 22.60 good 52.4 inferior 1.17 E33 A26-2 B3 good 0.14 good 1.26 good 2.23 E34 A27-2 good 0.16 good 1.25 good 2.28 C19 A26-2 B6 good 21.72 good 51.4 inferior 1.32 C20 A27-2 good 22.44 good 59.9 inferior 1.19 E35 A28-2 B3 good 0.15 good 1.22 good 2.32 E36 A29-2 good 0.13 good 1.29 good 2.24 C21 A28-2 B6 good 22.08 good 60.1 inferior 1.16 C22 A29-2 good 21.32 good 63.2 inferior 1.22

[0136] Table 4-2 Implementation / Comparative Example Number Actual selection capacitor @ 1MHz (pF) COVC tan δ @1 MHz insulation resistance (10¹² Ω) ESR @1 GHz (Ω) Q @1 GHz Water vapor intrusion failure rate E1 5.59 1.30% 2.50*10-4 3.57 0.128 218.7 0% E2 5.61 1.20% 1.50*10-4 3.57 0.108 243.0 0% E3 5.62 0.80% 1.00*10-4 5.33 0.104 252.4 0% E4 5.58 1.50% 2.00*10-4 2.23 0.135 194.4 0% E5 5.60 1.60% 2.80*10-4 5.63 0.138 190.0 0% C1 5.59 3.35% 5.10*10-4 0.857 0.213 123.2 20% C2 5.58 3.45% 6.10*10-4 0.562 0.223 119.3 25% E6 5.62 1.65% 3.20*10-4 2.97 0.113 228.3 0% E7 5.59 1.56% 1.30*10-4 3.85 0.106 237.1 0% E8 5.62 0.85% 1.10*10-4 6.32 0.098 255.9 0% E9 5.62 1.76% 2.20*10-4 3.33 0.135 185.8 0% E10 5.58 1.89% 3.10*10-4 3.83 0.157 159.7 0% C3 5.59 3.20% 5.60*10-4 0.927 0.193 129.9 35% E11 6.78 1.53% 3.00*10-4 6.56 0.110 187.6 0% E12 6.81 1.23% 1.30*10-4 5.67 0.106 228.0 0% E13 6.82 0.83% 8.90*10-5 7.35 0.098 216.3 0% E14 6.79 1.56% 1.30*10-4 5.23 0.135 207.8 0% E15 6.80 1.67% 2.80*10-4 2.76 0.157 196.3 0% C4 6.78 3.64% 5.70*10-4 0.567 0.183 115.8 25% E16 6.82 1.80% 2.50*10-4 8.95 0.108 196.1 0% E17 6.81 1.60% 1.40*10-4 4.53 0.108 196.7 0% E18 6.79 0.70% 9.00*10-5 5.69 0.095 223.1 0% E19 6.80 1.56% 2.10*10-4 4.62 0.141 150.3 0% C5 6.79 3.28% 5.80*10-4 0.892 0.188 112.6 30% E20 0.99 1.31% 1.25*10-4 5.69 0.267 586.5 0% C6 1.01 3.36% 5.40*10-4 4.39 0.328 477.4 10% E21 1.02 0.80% 1.40*10-4 5.69 0.232 675.0 0% C7 1.00 3.15% 5.20*10-4 3.98 0.287 545.6 10% E22 1.01 1.60% 2.10*10-4 5.28 0.223 702.2 0% E23 0.90 1.09% 2.30*10-4 8.67 0.256 611.7 0% C8 1.00 3.02% 5.00*10-4 4.84 0.253 618.9 30% C9 1.02 3.28% 5.70*10-4 5.43 0.296 529.0 10% E24 1.01 0.98% 9.21*10-5 5.43 0.201 779.1 0% E25 1.00 1.06% 9.52*10-5 7.89 0.198 790.9 0% C10 1.00 3.21% 5.13*10-4 3.59 0.267 586.5 30% C11 0.98 2.96% 5.70*10-4 6.89 0.256 611.7 20% E26 0.99 1.12% 2.35*10-4 3.35 0.235 666.3 0% E27 1.02 1.23% 2.46*10-4 6.24 0.241 649.8 0% C12 1.00 3.02% 5.10*10-4 1.12 0.288 543.7 20% C13 1.01 3.30% 5.70*10-4 3.39 0.301 520.2 10% E28 1.02 0.98% 1.68*10-4 8.23 0.223 702.2 0% C14 1.00 2.98% 5.30*10-4 6.69 0.289 541.8 30% E29 0.21 1.36% 4.60*10-4 8.53 0.581 1368.8 0% E30 0.21 1.39% 4.30*10-4 8.35 0.567 1402.6 0% C15 0.20 3.31% 8.60*10-4 5.23 0.678 1172.9 10% C16 0.21 3.11% 7.30*10-4 7.35 0.683 1164.4 10% E31 0.19 1.28% 4.40*10-4 9.85 0.575 1383.1 0% E32 0.20 1.25% 4.30*10-4 6.58 0.513 1550.2 0% C17 0.20 3.23% 8.30*10-4 8.85 0.672 1183.4 30% C18 0.19 3.19% 8.10*10-4 8.58 0.615 1293.1 30% E33 0.21 1.56% 3.50*10-4 8.28 0.532 1494.8 0% E34 0.20 1.19% 3.80*10-4 8.59 0.528 1506.2 0% C19 0.20 3.52% 7.51*10-4 3.28 0.635 1252.4 20% C20 0.21 3.31% 7.51*10-4 2.39 0.643 1236.8 30% E35 0.19 1.08% 3.60*10-5 8.33 0.487 1633.0 0% E36 0.19 1.06% 3.85*10-4 9.69 0.489 1626.3 0% C21 0.20 3.15% 7.90*10-4 4.36 0.556 1430.3 10% C22 0.21 3.21% 8.40*10-4 2.37 0.593 1341.1 30%

[0137] [Implementation Example] [3-T1] [To the Example] [3-T3(E3-T1)] [to] [E3-T3)] [Comparative Examples] [1-T1(C1-T1)] [Ceramic Electronic Components] [(] [Surface Adhesive] [RF-MLCC]

[0138] The methods used to prepare Examples 3-T1 to 3-T3 and Comparative Example 1-T1 are similar to those used to prepare the ceramic electronic components of Example 3 (especially the same composition (A), composition (B), and copper inner electrode layer composition (a)). The main difference is that since the screening capacitance of the samples of Examples 3-T1 to 3-T3 and Comparative Example 1-T1 is set to 2.20 ± 0.02 pF at 1 MHz, the number and / or thickness of the ceramic top cover layer, ceramic sub-layer, ceramic bottom cover layer, and inner electrode included in the ceramic body are adjusted to achieve the above screening capacitance value; and the highest temperature of the sintering step in forming the first terminal electrode paste of the composition (B) (using Preparation Example B3) is changed, as specifically described in Table 5-1.

[0139] Furthermore, Examples 3-T1 to 3-T3 and Comparative Example 1-T1 were tested according to the analytical methods described above, and the analytical results are recorded in Tables 5-1 and 5-2. The analysis results regarding the interface morphology between the first terminal electrode and the ceramic body are as follows: No glass floating was found at the first terminal electrode of the ceramic electronic components in Examples 3-T1 to 3-T3; however, glass floating was found at the first terminal electrode of the ceramic electronic component in Comparative Example 1-T1. No bubbles were found at the interface between the first terminal electrode and the ceramic body of the ceramic electronic components in Examples 3-T1 to 3-T3; however, bubbles were found at the interface between the first terminal electrode and the ceramic body of the ceramic electronic component in Comparative Example 1-T1.

[0140] Table 5-1 Example / Comparative Example Number Preparation example number of composition (A) Sintering temperature (°C) First terminal electrode Bond strength of flux layer (Kgf) Embryo formation Total glass area percentage (%) density resistivity (10⁻⁷ Ω·m) weldability E3-T2 A1-2 940±20 good 0.13 good 1.32 good 2.62 E3-T1 920±20 good 0.14 good 1.36 good 2.53 E3-T3 880±20 good 0.12 good 1.28 good 2.49 C1-T1 920±20 good 22.72 acceptable 78.4 inferior 1.14

[0141] Table 5-2 Example / Comparative Example Number Actual screening capacitor @1MHz (pF) COVC tan δ @1 MHz insulation resistance (10¹² Ω) ESR @1 GHz (Ω) Q @1 GHz Water vapor intrusion failure rate E3-T2 2.21 1.50% 1.00*10-4 7.87 0.166 418.1 0% E3-T1 2.22 1.30% 1.10*10-4 5.33 0.163 425.8 0% E3-T3 2.18 1.20% 1.30*10-4 6.89 0.164 423.2 0% C1-T1 2.18 3.20% 7.50*10-4 0.564 0.213 325.8 10%

[0142] [Example]

[37] [To the Example] [39(E37)] [to] [E39)] [Comparative Examples] [twenty three] [to] [25(C23)] [to] [C25) [Ceramic Electronic Components] [(] [Surface Adhesive] [RF-MLCC]

[0143] The methods used in the preparation of Examples 37 to 39 and Comparative Examples 23 to 25 are similar to those used in the preparation of the ceramic electronic components of Example 3 (especially the copper inner electrode layer composition (a) is the same). The main difference is that the preparation examples using the composition (A) and / or the composition (B) are different, as detailed in Table 6-1.

[0144] Furthermore, Examples 37 to 39 and Comparative Examples 23 to 25 were tested according to the analytical methods described above, and the analytical results are recorded in Tables 6-1 and 6-2. The analysis results regarding the interface morphology between the first terminal electrode and the ceramic body are as follows: No glass float-out phenomenon was found at the first terminal electrode of the ceramic electronic components in Examples 37 to 39; however, glass float-out phenomenon was found at the first terminal electrode of the ceramic electronic components in Comparative Examples 23 to 25. No bubbles were found at the interface between the first terminal electrode and the ceramic body of the ceramic electronic components in Examples 37 to 39; however, bubbles were found at the interface between the first terminal electrode and the ceramic body of the ceramic electronic components in Comparative Examples 23 to 25.

[0145] Table 6-1 Example / Comparative Example Number Preparation example number of composition (A) Preparation example number of composition (B) First terminal electrode Bond strength of flux layer (Kgf) Embryo formation Total glass area percentage (%) density resistivity (10⁻⁷ Ω·m) weldability E37 A3-2 B3 good 0.07 good 1.29 good 2.58 E3 A1-2 good 0.13 good 1.28 good 2.27 E38 A4-2 good 0.14 good 1.25 good 2.28 E39 A5-2 good 0.16 good 2.87 good 2.10 C23 A3-2 B6 good 22.60 good 36.7 inferior 1.35 C24 A4-2 good 23.36 good 85.0 inferior 1.15 C25 A5-2 good 23.52 good 83.8 inferior 1.08

[0146] Table 6-2 Implementation / Comparative Example Number Actual selection capacitor @ 1MHz (pF) COVC tan δ @1 MHz Absolute Fate resistance (10¹² Ω) ESR @1 GHz (Ω) Q @1 GHz Water vapor intrusion failure rate E37 5.62 1.25% 2.50*10-4 3.57 0.115 232.8 0% E3 5.62 0.80% 1.00*10-4 5.33 0.104 252.4 0% E38 5.62 1.22% 1.60*10-4 5.89 0.123 217.7 0% E39 5.58 1.50% 2.80*10-4 2.23 0.135 198.3 0% C23 5.62 3.32% 5.21*10-4 9.73 0.218 122.8 25% C24 5.59 3.58% 6.50*10-4 7.37 0.253 105.8 25% C25 5.61 3.67% 6.81*10-4 6.57 0.257 104.2 30%

[0147] [Example]

[40] [to] [44(E40)] [to] [E44)] [Comparative Examples] [26(C26)] [Ceramic Electronic Components] [(] [Embedded type] [RF-MLCC]

[0148] The methods used to prepare Examples 40 to 44 are similar to those used to prepare the ceramic electronic components of Examples 1 to 5 (especially the same composition (A), composition (B), and copper inner electrode layer composition (a)). The main difference is that the ceramic electronic components of Examples 40 to 44 do not include two second end electrodes and two flux layers plated on the surface of the first end electrode; that is, the ceramic electronic components of Examples 40 to 44 are as shown in Figure 1 instead of Figure 2.

[0149] Specifically, firstly, according to Table 7-1, each embodiment further prepares a ceramic body from the ceramic ribbon formed by the composition (A) of the specific preparation example obtained according to Table 2-3: multiple identical ceramic ribbons with a specific thickness (approximately 15 μm) are prepared by coating molding of the ceramic slurry (i.e., after subsequent sintering, they are distinguished into a ceramic upper cover layer, a ceramic sub-layer, and a ceramic lower cover layer according to their position in the ceramic body). Next, the aforementioned copper inner electrode layer composition (a) is coated onto the upper surface of a portion of the ceramic ribbons by screen printing. The remaining ceramic ribbons without the aforementioned copper inner electrode layer composition (a) are referred to as blank ceramic ribbons. Then, in a stacking apparatus, some blank ceramic strips are first placed at the bottom (to form a ceramic lower cover layer); next, ceramic strips coated with copper internal electrode layer composition (a) are sequentially stacked (the copper internal electrode layer composition (a) is always facing upwards); finally, some blank ceramic strips are placed at the top (to form a ceramic upper cover layer) to form a stacked structure. Next, the aforementioned stacked structure is subjected to an equalization step and a cutting step to form a green embryo. Next, the green body undergoes a debinding step and a sintering step in sequence to obtain a sintered ceramic body. The debinding step includes heating to 500±10°C at a slow rate (0.5°C / min to 1°C / min), holding at this temperature for 4 hours, and then cooling to 40°C. The total time of the debinding step (BBO) is approximately 48 hours (including overall heating, high-temperature holding, and cooling). The sintering step is performed in a nitrogen atmosphere (oxygen content of 1 ppm to 100 ppm) at a sintering temperature of 950±20°C for 2 hours. The sintering step includes heating to 950±20°C at a slow rate (15°C / min to 30°C / min), holding at this temperature for 15 minutes, and then cooling to room temperature (the total time is approximately 1.5 hours). Then, according to Table 7-1, the first end electrode paste formed by the composition (B) of the specific preparation example prepared according to Table 3 is impregnated on the opposite two end faces of the sintered body of the ceramic body, and then a sintering step is performed under a protective atmosphere; wherein, the sintering step first goes through a debinding stage (at a temperature of 650°C for 30 minutes under a nitrogen atmosphere with an oxygen content of less than 10 ppm), followed by a sintering stage (at a maximum temperature of 920±20°C for 30 minutes under a nitrogen atmosphere with an oxygen content of less than 5 ppm) to form the two first end electrodes on the opposite two end faces (i.e., the first end face and the second end face) of the sintered body of the ceramic body, and finally the ceramic electronic components of Examples 40 to 44 are obtained. The dimensions of the ceramic electronic components are as follows: length 0.6±0.03 mm × width 0.3±0.03 mm × thickness 0.3±0.03 mm.To further explain, the ceramic electronic components of Examples 40 to 44 had their respective ceramic upper and lower cover layers adjusted according to the target capacitance value and the number and thickness of the aforementioned ceramic sublayers and internal electrodes. To ensure more accurate subsequent ESR measurements, the screening capacitance of the samples in Examples 40 to 44 was set to 4.7 ± 0.02 pF at 1 MHz, and the actual screening capacitance values ​​for each group are recorded in Table 7-2.

[0150] Similarly, the method used to prepare Comparative Example 26 is similar to the method used to prepare the ceramic electronic component of Example 40 (especially the composition (A) and the copper inner electrode layer composition (a) are the same), the main difference being that the composition (B) used in Comparative Example 26 is the same as the composition (B) of Preparation Example B6.

[0151] In addition, Examples 40 to 44 and Comparative Example 26 were tested for their first terminal electrodes according to the analytical methods described above, including green moldability, total glass area ratio, density, interface morphology with the ceramic body (observation of glass floating and air bubbles at the interface), and resistivity. The ceramic electronic components were also tested for COVC, dielectric loss at 1 MHz, insulation resistance, equivalent series resistance and quality factor at 1 GHz, and water vapor intrusion failure rate. The analysis results are recorded in Tables 7-1 and 7-2. Regarding the interface morphology between the first terminal electrode and the ceramic body, the analysis results are as follows: no glass floating was found in the first terminal electrodes of the ceramic electronic components of Examples 40 to 44; however, glass floating was found in the first terminal electrode of the ceramic electronic component of Comparative Example 26. No air bubbles were found at the interface between the first terminal electrode and the ceramic body of the ceramic electronic components of Examples 40 to 44; however, air bubbles were found at the interface between the first terminal electrode and the ceramic body of the ceramic electronic component of Comparative Example 26.

[0152] In addition, the ceramic electronic components of Examples 40 to 44 and Comparative Example 26 were also subjected to adhesion test failure rate analysis, as detailed below.

[0153] [analyze]

[17] [Adhesion] (Adhesion) [Test failure rate] [ ]

[0154] According to the JISC5201-1 4.25.3 standard method, adhesion tests were performed on samples of ceramic electronic components in Examples 40 to 44 and Comparative Example 26. The samples were soldered onto a PCB board and shear force was applied to the side. The applied force was a lateral force (3 Newtons (N)) for 10 ± 1 seconds. The adhesion was evaluated by assessing whether the first electrode of the sample peeled off or detached. If the above conditions were found, the sample was judged as "failure". Ten identical ceramic electronic components were measured in each group, and the failure rate was recorded as the "percentage of failures out of the total number of failures".

[0155] Table 7-1 Example / Comparative Example Number Preparation example number of composition (A) Preparation example number of composition (B) First terminal electrode Adhesion test failure rate Embryo formation Total glass area percentage (%) density resistivity (10⁻⁷ Ω·m) E40 A1-2 B1 good 0.13 good 1.25 0% E41 B2 good 0.13 good 1.32 0% E42 B3 good 0.12 good 1.22 0% E43 B4 good 0.11 good 2.85 0% E44 B5 good 0.11 good 3.15 0% C26 B6 good 23.36 Difference 68.9 30%

[0156] Table 7-2 Example / Comparative Example Number Actual screening capacitor @1MHz (pF) COVC tan δ @1 MHz insulation resistance (10¹² Ω) ESR @1 GHz (Ω) Q @1 GHz Water vapor intrusion failure rate E40 4.72 1.00% 2.05*10-4 8.26 0.115 282.7 0% E41 4.68 1.32% 1.10*10-4 8.57 0.097 335.2 0% E42 4.69 0.89% 9.80*10-5 0.943 0.098 331.8 0% E43 4.71 1.56% 1.20*10-4 7.67 0.110 295.6 0% E44 4.68 1.80% 2.30*10-4 5.23 0.158 205.8 0% C26 4.69 3.43% 5.75*10-4 0.878 0.263 123.6 10%

[0157] [Example]

[45] [to] [47(E45)] [to] [E47)] [Comparative Examples] [27(C27)] [Ceramic Electronic Components] [(] [Thin Embedded Connector Components] [)]

[0158] First, according to Table 8-1, Examples 45 to 47 and Comparative Example 27 are ceramic bodies further prepared from ceramic ribbons formed by the specific preparation examples (A) prepared according to Table 2-3: multiple identical ceramic ribbons with a specific thickness (approximately 6 μm) are prepared by coating molding method from the ceramic slurry (i.e., after subsequent sintering, they are distinguished into a ceramic upper cover layer, a ceramic sub-layer, and a ceramic lower cover layer according to their position in the ceramic body). Next, the copper inner electrode layer composition (a) is coated onto the upper surface of a portion of the ceramic ribbons by screen printing method. The remaining ceramic ribbons without the aforementioned copper inner electrode layer composition (a) are referred to as blank ceramic ribbons. Then, in a stacking apparatus, some blank ceramic strips are first placed at the bottom (to form a ceramic lower cover layer); next, 12 ceramic strips coated with copper inner electrode layer composition (a) are sequentially stacked (the electrode layer composition is always facing upwards); finally, some blank ceramic strips are placed at the top (to form a ceramic upper cover layer) to form a stacked structure. Next, the aforementioned stacked structure is subjected to a pressure equalization step and a cutting step to form a green body. Then, the green body undergoes a debinding step and a sintering step to obtain a sintered ceramic body (also known as a mature green body). The aforementioned debonding step includes heating to 500±10°C at a slow rate (0.5°C / min to 1°C / min), holding at this temperature for 4 hours, and then cooling to 40°C; the total time of the debonding step (BBO) is approximately 48 hours (including overall heating, high-temperature holding, and cooling); the aforementioned sintering step includes sintering at 950±20°C in a nitrogen atmosphere (oxygen content of 1 ppm) for 2 hours; the sintering step includes heating to 920±20°C at a slow rate (15°C / min to 30°C / min), holding at this temperature for 15 minutes, and then cooling to room temperature; the total time of the sintering step is approximately 1.5 hours (including overall heating, high-temperature holding, and cooling). The internal electrode has a total of 12 layers with a thickness of 2.1 ± 0.1 μm, while the ceramic sublayer has a thickness of 5.1 ± 0.2 mm.

[0159] Then, according to Table 8-1, the first end electrode paste formed by the composition (B) of the specific preparation example prepared according to Table 3 is impregnated on the opposite two end faces of the sintered body of the ceramic body, and then a sintering step is performed under a protective atmosphere; wherein, the sintering step first goes through a debinding stage (at a temperature of 650°C for 30 minutes under a nitrogen atmosphere with an oxygen content of less than 10 ppm), followed by a sintering stage (at a maximum temperature of 920°C for 30 minutes under a nitrogen atmosphere with an oxygen content of less than 5 ppm) to form the two first end electrodes on the opposite two end faces (i.e., the first end face and the second end face) of the sintered body of the ceramic body, and finally the ceramic electronic components of Examples 45 to 47 and Comparative Example 27 are obtained. The dimensions of the ceramic electronic components are as follows: length 0.6±0.03 mm × width 0.3±0.03 mm × thickness 0.3±0.03 mm.

[0160] Please refer to Figures 5A to 5C. The ceramic electronic component 1 of embodiments 45 to 47 includes a ceramic body 10 and two first end electrodes 20. The ceramic body 10 has a first end face 101 and a second end face 102 that are opposite to each other. The ceramic body 10 includes a plurality of ceramic sublayers 11 and a plurality of inner electrodes 12. The ceramic sublayers 11 and the inner electrodes 12 are alternately stacked within the ceramic body 10. In addition, the ceramic body 10 also includes a ceramic upper cover layer 13 and a ceramic lower cover layer 14, which sandwich the stacked layers of ceramic sublayers 11 and inner electrodes 12. Since the length of each inner electrode 12 is the same as the length of the ceramic body 10, that is, the parallel distance between the first end face 101 and the second end face 102, each inner electrode 12 can be connected to the two first end electrodes 20. The two first end electrodes 20 respectively cover the first end face 101 and the second end face 102 of the ceramic body 10, and are both electrically connected to the inner electrodes 12. Similarly, although the number of inner electrode layers 12 shown in FIG. 5A is 10, the number of ceramic sublayers 11 and inner electrodes 12 in the figure is mainly for illustrative purposes and does not represent the actual number contained in the aforementioned ceramic electronic components.

[0161] In addition, the ceramic electronic components of Examples 45 to 47 and Comparative Example 27 were tested for their first end electrodes using the analytical methods described above, including green moldability, total glass area ratio, density, interface morphology with the ceramic body (observation of glass floating and presence of bubbles at the interface), resistivity, and adhesion failure rate. Furthermore, the ceramic electronic components were tested for resistance, COVR, bending failure rate, short-term instantaneous load failure rate, and moisture intrusion failure rate, and the analysis results are recorded in Tables 8-1 and 8-2. Regarding the analysis results of the interface morphology between the first end electrode and the ceramic body: no glass floating was found in the first end electrodes of the ceramic electronic components of Examples 45 to 47; however, glass floating was found in the first end electrode of the ceramic electronic component of Comparative Example 27. No bubbles were found at the interface between the first end electrode and the ceramic body of the ceramic electronic components of Examples 45 to 47; however, bubbles were found at the interface between the first end electrode and the ceramic body of the ceramic electronic component of Comparative Example 27.

[0162] [analyze]

[18] [Bending Failure Rate Analysis]

[0163] According to JIS C 5201-1:Clause 4.33, the ceramic electronic components of Examples 45 to 47 and Comparative Example 27 were first mounted on a 90 mm standard grade FR-4 copper-clad laminate to prepare test samples. Next, the test samples were pressed down using a universal testing machine (manufacturer: Qualitest, model: QM-2001F), and their appearance and metallographic cross-section were observed using a metallographic microscope (manufacturer: OLYMPUS, model: BX60M) to assess the breakage rate based on the cross-section (i.e., 100%). The relevant parameters for this analysis are as follows: indenter curvature radius R5, pressing rate 1.0 mm / s, bending displacement of the test sample 3 mm, duration 10 ± 1 seconds, and number of samples measured 10. The average value was recorded in Table 8-2.

[0164] [analyze]

[19] [Short-term instantaneous load failure rate]

[0165] First, the ceramic electronic components of Examples 45 to 47 and Comparative Example 27 were soldered onto a test board. According to the JIS C 5201-1:Clause 4.13 test specification, a current (2.5 amps) was applied to each group of test samples in a chip resistor STOL test system using a power supply (manufacturer: Keysight Technologies Co., Ltd., model: E3640A) that was cyclically switched on and off (5 seconds on, 5 seconds off). The resistance was observed to see if the high current caused the component to melt, resulting in an open circuit, or if its resistance rose above 50 mΩ. If any of these conditions were present, the component was considered "failed." For each group, 100 identical ceramic electronic components were measured, and the failure rate was calculated as the percentage of failures out of the total. For example, if there were 2 failures, the failure rate was 2 / 100 = 2%.

[0166] If the obtained short-term instantaneous load failure rate is 0%, its reliability is rated as "good"; if the obtained short-term instantaneous load failure rate is greater than 0% and less than or equal to 15%, its reliability is rated as "fair"; if the obtained short-term instantaneous load failure rate is greater than 15%, its reliability is rated as "poor".

[0167] [Example]

[48] [to] [50(E48)] [to] [E50)] [Comparative Examples] [28(C28)] [Ceramic Electronic Components] [(] [Surface Mount Connector Components] [)]

[0168] The methods used in preparing Examples 48 to 50 and Comparative Example 28 are similar to those used in preparing ceramic electronic components in Examples 45 to 47 and Comparative Example 27. The main difference is that (1) the ceramic electronic component further includes two second terminal electrodes and two flux layers; wherein, the two second terminal electrodes are respectively formed on the outer surface of the two first terminal electrodes, and the two flux layers are respectively formed on the outer surface of the two second terminal electrodes; that is, the first end face and the second end face of the ceramic body are sequentially covered by the first terminal electrode, the second terminal electrode and the flux layer from the inside to the outside. Furthermore, the ceramic electronic components of Examples 48 to 50 and Comparative Example 28 contain a total of 27 layers of internal electrodes with a thickness of 2.2 ± 0.1 μm, while the thickness of the ceramic sublayer is 5.6 ± 0.2 mm. Therefore, the ceramic electronic components of Examples 48 to 50 and Comparative Example 28 have the following dimensions: length 0.6 ± 0.03 mm × width 0.3 ± 0.03 mm × thickness 0.23 ± 0.03 mm.

[0169] Referring to Figure 6, the ceramic electronic component 1 of embodiments 48 to 50 includes a ceramic body 10 and two first end electrodes 20; wherein the ceramic body 10 has a first end face 101 and a second end face 102 opposite to each other. Furthermore, the ceramic body 10 includes a plurality of ceramic sublayers 11 and a plurality of inner electrodes 12; wherein the ceramic sublayers 11 and the inner electrodes 12 are alternately stacked within the ceramic body 10; in addition, the ceramic body 10 also includes a ceramic upper cover layer 13 and a ceramic lower cover layer 14, wherein the ceramic upper cover layer 13 and the ceramic lower cover layer 14 sandwich the stacked layers formed by the alternate stacking of the ceramic sublayers 11 and the inner electrodes 12. Since the length of each inner electrode 12 is the same as the length of the ceramic body 10, that is, the parallel distance between the first end face 101 and the second end face 102, each inner electrode 12 can be connected to the two first end electrodes 20. The two first end electrodes 20 respectively cover the first end face 101 and the second end face 102 of the ceramic body 10, and are electrically connected to the inner electrodes 12. Two second end electrodes 30 are respectively formed on the outer surface of the two first end electrodes 20, and two flux layers 40 are respectively formed on the outer surface of the two second end electrodes 30. That is to say, the first end face 101 and the second end face 102 of the ceramic body 10 are sequentially covered by the first end electrode 20, the second end electrode 30 and the flux layer 40 from the inside out. Similarly, although the number of inner electrode layers 12 shown in FIG. 6 is 10, the number of ceramic sub-layers 11 and inner electrodes 12 in the figure is mainly for illustration purposes and is not the actual number contained in the aforementioned ceramic electronic components.

[0170] In addition, the ceramic electronic components of Examples 48 to 50 and Comparative Example 28 were analyzed using the methods described above to test the green moldability, total glass area ratio, density, interface morphology with the ceramic body (observing whether glass floats out and whether there are bubbles at the interface), resistivity, solderability, and bonding strength of the flux layer of their first end electrodes. Furthermore, the ceramic electronic components were tested for resistance, COVR, bending failure rate, short-time instantaneous load failure rate, and moisture intrusion failure rate, and the analysis results are recorded in Tables 8-1 and 8-2. Regarding the analysis results of the interface morphology between the first end electrode and the ceramic body: no glass floats were found at the first end electrode of the ceramic electronic components of Examples 48 to 50; however, glass floats were found at the first end electrode of the ceramic electronic component of Comparative Example 28. No bubbles were found at the interface between the first end electrode and the ceramic body of the ceramic electronic components of Examples 48 to 50; however, bubbles were found at the interface between the ceramic electronic component and the ceramic body of Comparative Example 28.

[0171] Table 8-1 Example / Comparative Example Number Preparation example number of composition (A) Preparation example number of composition (B) First terminal electrode Adhesion test failure rate Bond strength of flux layer (Kgf) Embryo formation Total glass area percentage (%) density resistivity (10⁻⁷ Ω·m) weldability E45 A1-2 B1 acceptable 0.13 good 1.20 -- 0% -- E46 B3 good 0.14 good 1.18 -- 0% -- E47 B5 good 0.11 acceptable 2.90 -- 0% -- C27 B6 good 22.76 acceptable 75.4 -- 10% -- E48 A1-2 B1 acceptable 0.12 good 1.32 good -- 2.34 E49 B3 good 0.13 good 1.28 good -- 2.27 E50 B5 good 0.11 acceptable 3.14 good -- 1.53 C28 B6 good 22.96 acceptable 65.4 inferior -- 1.10

[0172] Table 8-2 Implementation / Comparative Example Number resistance value (mΩ) COVR Bending failure rate (%) Instantaneous load failure rate (%) Water vapor intrusion failure rate E45 9.3 2.00% 0% 0% 0% E46 8.5 1.08% 0% 0% 0% E47 9.1 1.31% 0% 0% 0% C27 20.5 3.23% 20% 0% 10% E48 2.5 2.00% 0% 0% 0% E49 1.5 0.82% 0% 0% 0% E50 2.3 1.38% 0% 0% 0% C28 5.3 3.53% 0% 0% 10%

[0173] [Circuit board] [(I)]

[0174] As shown in Figure 7, a first embodiment of the circuit board of this invention can be a circuit board P containing an embedded ceramic electronic component 1 (a conventional printed circuit board can be used, but is not limited to this). The circuit board P includes a ceramic electronic component 1 and a dielectric substrate S1, wherein the ceramic electronic component 1 is embedded in the dielectric substrate S1; and the dielectric substrate S1 includes a conductive pattern C1 and a plurality of through-hole conductors TH. The ceramic electronic component 1 is connected to the conductive pattern C1 of the dielectric substrate S1 through the through-hole conductors TH. Other electronic components 2 besides the ceramic electronic component 1 can be connected to the surface of the circuit board P. The electronic components 2 can be active components (e.g., packaged semiconductor IC chips, but not limited to this) or passive components (e.g., capacitors, but not limited to this). The electronic components 2 can be connected to the circuit board P by solder 3 (tin).

[0175] [Circuit board] [(II)]

[0176] As shown in Figure 8, a second embodiment of the circuit board of this invention can be a circuit board P containing a surface-mount ceramic electronic component 1 (a low-temperature co-fired ceramic circuit board can be used, but is not limited to this). The circuit board P includes the ceramic electronic component 1 and a substrate S2 provided with electrodes E and through-hole conductors TH; the two solder layers 40 in the ceramic electronic component 1 are connected to the electrodes E of the substrate S2 by solder, and the electrodes E are connected to the through-hole conductors TH, thereby forming a module with a specific function.

[0177] [Ceramic Electronic Components]

[0178] The ceramic electronic component of this invention may also have other configurations, such as the ceramic electronic component 1' shown in Figure 9. The ceramic electronic component 1' includes: a ceramic body 10' having a first end face 101'; two first end electrodes 20' disposed on the first end face 101' of the ceramic body 10'; and two conductor connectors (in this embodiment, through-hole conductors TH), each of the two through-hole conductors TH being disposed in the ceramic body 10', and each through-hole conductor TH contacting the two first end electrodes 20'. The ceramic body 10' includes: a plurality of ceramic sublayers 11' and a plurality of inner electrodes 12'; wherein the ceramic sublayers 11' and the inner electrodes 12' are alternately stacked within the ceramic body 10'; each inner electrode 12' is connected to the two through-hole conductors TH, and the inner electrode 12' is electrically connected to the two first end electrodes 20'.

[0179] In addition, the ceramic electronic component 1' also includes two second terminal electrodes 30' and two solder flux layers 40'; the two second terminal electrodes 30' are respectively formed on the outer surface of the two first terminal electrodes 20', and the two solder flux layers 40' are respectively formed on the outer surface of the two second terminal electrodes 30'.

[0180] [Example]

[51] [to] [53(E51)] [to] [E53)] [Comparative Examples] [29(C29)] [:] [Low-temperature co-fired ceramics] [Simulated sample of circuit board]

[0181] First, as shown in Figure 9 and Table 9-1, each embodiment further prepares a ceramic body 10' from the ceramic strip formed by the specific preparation example composition (A) prepared according to Table 2-3: multiple identical ceramic strips with a specific thickness (approximately 15 μm) are prepared by coating molding method (i.e., after subsequent sintering, they are distinguished as a ceramic upper cover layer, a ceramic sub-layer 11', and a ceramic lower cover layer according to their position in the ceramic body 10'). Next, the aforementioned copper inner electrode layer composition (a) is coated onto the upper surface of a portion of the ceramic strips by screen printing method, and the remaining ceramic strips without the aforementioned copper inner electrode layer composition (a) are referred to as blank ceramic strips. Then, in a stacking device, some blank ceramic strips are first placed at the bottom (to form a ceramic underlayer); then, three ceramic strips coated with copper inner electrode layer composition (a) are sequentially stacked (the copper inner electrode layer composition (a) is always facing upwards) and pre-laser-perforated strips are then filled into the through holes to fill the aforementioned copper inner electrode layer composition (a); then, multiple cylindrical through-hole conductors TH are manufactured in a stacking alignment manner and connected to the inner electrode 12' so that it can be subsequently connected from the inside to the external conductive pattern; next, the aforementioned stacked structure is subjected to an equalization step. Next, the aforementioned stacked structure is cut to form a green body; the green body is then subjected to a debinding step and a sintering step to obtain a sintered ceramic body 10'; wherein, the aforementioned debinding step includes heating to 500±10°C at a slow heating rate (0.5°C / min to 1°C / min), holding at this temperature for 4 hours, and then cooling to 40°C; the total time of the debinding step (BBO) is approximately 48 hours (including overall heating, high-temperature holding, and cooling); the aforementioned sintering step is performed in a nitrogen atmosphere (oxygen content of 1 ppm) at a sintering temperature of 950±20°C, and held at the aforementioned sintering temperature for 2 hours; the sintering step includes heating to 950±20°C at a slow heating rate (15°C / min to 30°C / min), holding at this temperature for 15 minutes, and then cooling to room temperature (the total time is approximately 1.5 hours). Next, the acute angle of the sintered body of the ceramic body 10' is removed.Then, according to Table 9-1, the first end electrode paste formed by the composition (B) of the specific preparation example prepared according to Table 3 is applied by roller coating (or by adsorption or printing) to at least two regions on the first end face 101' of the sintered body of the ceramic body 10', where the through-hole conductors TH are located below the regions, that is, the first end electrode paste is in direct contact with the through-hole conductors TH; next, a sintering step is performed under a protective atmosphere; wherein the sintering step first undergoes a desizing stage (at a nitrogen atmosphere with an oxygen content of less than 1 ppm, at a temperature of 650°C, held for 30 minutes), followed by a sintering stage (at a nitrogen atmosphere with an oxygen content of less than 5 ppm, at a temperature of 650°C, held for 30 minutes), and then a sintering stage (at a nitrogen atmosphere with an oxygen content of less than 5 ppm, at a temperature of 650°C, held for 30 minutes). Under a nitrogen atmosphere of ppm, at a maximum temperature of 920±20°C and held for 30 minutes, the two first end electrodes 20' were formed on one end face (i.e., first end face 101') of the sintered body of the ceramic body 10'. Finally, the ceramic electronic component 1' contained in the simulated samples of the low-temperature co-fired ceramic circuit board of Examples 51 to 53 was obtained. The dimensions of the ceramic electronic component 1' are as follows: length 1.6±0.2 mm × width 0.8±0.2 mm × thickness 0.8±0.2 mm; the inner electrode 12' has a total of 3 layers, with a thickness of 12.1±0.5 μm, a width of 600±10 μm, and a length of 1000±10 μm; the thickness of the ceramic sublayer 11' is 22.3±0.5 μm; the diameter of the cylindrical through-hole conductor TH (i.e., conductor connector) is 100.0±0.5 μm.

[0182] The ceramic electronic component 1' is configured as a simulated LTCC substrate and component; wherein, the diameter of the first terminal electrode 20' is 150±5 μm and the thickness is 25±3 μm; the thickness of the nickel layer (i.e., the second terminal electrode 30') formed by electroplating on the outer surface of the first terminal electrode 20' is 3±1 μm, and the thickness of the tin layer (i.e., the solder flux layer 40') formed by electroplating on the outer surface of the aforementioned nickel layer is 8±2 μm. Examples 51 to 53 first use simplified simulated samples as conductor connection lines, the main purpose of which is to predict the performance of subsequently manufactured capacitors, inductors, filters, etc., when placed in a complete LTCC component after testing the performance of the terminal electrodes.

[0183] The ceramic electronic components of Examples 51 to 53 and Comparative Example 29 were analyzed using the methods described above to determine the green moldability, total glass area ratio, density, interface morphology with the ceramic body (observation of glass floating and air bubbles at the interface), resistivity, and adhesion failure rate of their first terminal electrodes. Additionally, the simulated samples were tested for resistance, COVR, short-term instantaneous load failure rate, and water vapor intrusion failure rate, and the analysis results are recorded in Tables 9-1 and 9-2. The analysis results regarding the interface morphology between the first terminal electrode and the ceramic body are as follows: no glass floating was observed in the first terminal electrodes of the simulated low-temperature co-fired ceramic circuit boards of Examples 51 to 53; however, glass floating was observed in the first terminal electrode of the simulated low-temperature co-fired ceramic circuit board of Comparative Example 29. No air bubbles were found at the interface between the first terminal electrode and the ceramic body of the simulated low-temperature co-fired ceramic circuit boards of Examples 51 to 53; however, air bubbles were found at the interface between the first terminal electrode and the ceramic body of the simulated low-temperature co-fired ceramic circuit board of Comparative Example 29.

[0184] Table 9-1 Example / Comparative Example Number Preparation example number of composition (A) Preparation example number of composition (B) First terminal electrode Adhesion test failure rate Bond strength of flux layer (Kgf) Embryo formation Total glass area percentage (%) density resistivity (10⁻⁷ Ω·m) weldability E51 A1-2 B1 acceptable 0.13 good 1.25 -- 0% -- E52 B3 good 0.14 good 1.15 -- 0% -- E53 B5 good 0.11 good 2.72 -- 0% -- C29 B6 good 22.56 acceptable 75.4 -- 10% --

[0185] Table 9-2 Example / Comparative Example Number resistance value (mΩ) COVR Instantaneous load failure rate Water vapor intrusion failure rate E51 1.8 1.33% 0% 0% E52 1.0 1.18% 0% 0% E53 2.0 1.55% 0% 0% C29 5.3 3.29% 0% 10%

[0186] [Discussion of Experimental Results]

[0187] Even though the dielectric analysis of preparation examples A1 to A30 mainly focused on the simulation analysis of the ceramic layer, the experimental results in Table 2-2 clearly show that the specific main powder materials (barium titanate microwave dielectric oxide and calcium zirconate microwave dielectric oxide) used in this invention have good dielectric properties. Furthermore, the dielectric loss can be further reduced when the barium titanate microwave dielectric oxide is doped with the aforementioned dopant, or when the calcium zirconate microwave dielectric oxide is simultaneously doped with Sr and Mn elements.

[0188] Based on the analysis results of the total glass area ratio in Tables 4-1, 5-1, 6-1, 7-1, 8-1, and 9-1, it can be seen that the composition (B) used to form the first terminal electrode in the material for preparing ceramic electronic components of this invention contains no more than 3% by weight of glass material (the composition (B) in Examples 1 to 53 does not contain glass material). Therefore, although the first terminal electrode contains some glass components (the proportion of glass components to the total cross-sectional area of ​​the first terminal electrode is no more than 1%, or even less than 0.18%), no problem of glass overflowing from the predetermined coating surface or accumulating at the interface between the first terminal electrode and the ceramic body occurs during the firing process of forming the first terminal electrode. Furthermore, based on the analysis results in Tables 4-1, 5-1, 6-1, 7-1, 8-1, and 9-1, it can be seen that the first end electrodes formed by compositions (B) of Examples 1 to 53 exhibit better compactness, significantly lower resistivity, and greater ultimate tensile strength or lower adhesion test failure rate compared to the first end electrodes formed by compositions (B) of Comparative Examples 1, 3 to 29. This demonstrates that composition (B) in the materials for preparing ceramic electronic components of this invention, because it does not contain glass materials, does indeed provide better conductivity and better bonding with the ceramic body, thereby improving the yield of the final ceramic electronic component product. Moreover, the first end electrodes formed by compositions (B) of Examples 1 to 53 also avoid defects such as bubble formation and glass aggregation at the interface, thus improving solderability and ensuring good continuity of the subsequent electroplated layers (second end electrode, flux layer). In contrast, the first end electrodes formed by compositions (B) of Comparative Examples 1 to 29 all exhibited glass floating, and noticeable bubbles were present at the interface between the first end electrode and the ceramic body. Therefore, when these comparative examples underwent subsequent electroplating, the continuity of the second end electrodes formed was poor, and even breakage occurred. Furthermore, although the composition (B) used in the ceramic electronic component of Comparative Example 2 also did not contain glass material, the glass material in the composition (A) used in Comparative Example 2 had a low affinity for Cu / Cu2O (its contact angle with the Cu / Cu2O substrate was greater than 20° after the 880°C sintering process). Therefore, although the first end electrode formed also did not exhibit glass floating or bubble formation, its solderability was still poor, and the density and conductivity of the formed first end electrode were also significantly poor. This demonstrates that the composition (A) specified in this invention must contain a glass material with high affinity for copper and / or cuprous oxide to reliably utilize capillary action to extend from the ceramic body to the copper-containing first end electrode.

[0189] The COVC or COVR analysis results in Tables 4-2, 5-2, 6-2, 7-2, 8-2, and 9-2 show that the COVC or COVR of the ceramic electronic components in Examples 1 to 50 and the simulated samples of the low-temperature co-fired ceramic circuit boards in Examples 51 to 53 are all less than 3%, indicating good electrical stability. Especially in high-Q RF-MLCCs, which are widely used in wireless communication equipment such as filters, matching circuits, and coupling circuits, lower resistance tolerances better ensure the efficiency, stability, and signal integrity of the signal circuit. Therefore, it can be proven that the ceramic electronic components and the low-temperature co-fired ceramic circuit boards containing them are suitable for high-frequency, high-performance electronic products.

[0190] Furthermore, a comparison of the insulation resistance analysis results of the ceramic electronic components (RF-MLCCs) of Examples 1 to 44 and Comparative Examples 1 to 26 shows that, under the same composition (A), the ceramic electronic component of this invention has a higher insulation resistance. Therefore, the ceramic electronic component (capacitor) has a smaller leakage current under operating voltage and is better able to withstand voltage stress and current carrying capacity under high voltage or high temperature environments, is less prone to dielectric breakdown, and has better reliability and service life. In addition, a comparison of the ESR and quality factor analysis results of the ceramic electronic components (RF-MLCCs) of Examples 1 to 44 and Comparative Examples 1 to 26 shows that, under the same composition (A), the ceramic electronic component of this invention has a smaller ESR and a higher quality factor. This proves that the first terminal electrode of this invention does indeed have high density and good bonding with the ceramic body, thus reducing the internal resistance of the ceramic electronic component, transmission loss during use, and heat generation problems.

[0191] Based on the analysis results of water vapor intrusion failure rate in Tables 4-2, 5-2, 6-2, 7-2, 8-2, and 9-2, it can be seen that the water vapor intrusion failure rate of the ceramic electronic components in Examples 1 to 50 and the simulated samples of low-temperature co-fired ceramic circuit boards in Examples 51 to 53 is 0. When water vapor penetrates into the ceramic body, especially along defects in the ceramic sublayer (dielectric layer) or at the interface between the terminal electrode and the ceramic body, the water vapor acts as an electrolyte. If a DC voltage is applied simultaneously, the electric field drives the migration of ions in the electrode material. These metal ions move to the other electrode under the influence of the electric field and form conductive dendritic structures in or on the surface of the dielectric layer; or, water vapor intrusion at the terminal electrode leads to an increase in leakage current, ultimately causing a short circuit or a significant increase in leakage current in the ceramic electronic component. Therefore, it can be demonstrated that the first terminal electrode made from the material used to prepare the ceramic electronic component in this invention is not only dense itself but also has better bonding with the ceramic body, thus improving the reliability of the ceramic electronic component and making it more suitable for various environments (such as high-heat or high-humidity environments).

[0192] Furthermore, the bending failure rate analysis results in Table 8-2 show that the ceramic electronic component of this invention has excellent bending resistance, which means that no brittle intermetallic compound (IMC) is generated at the interface between the first terminal electrode and the ceramic body, thus reducing its failure risk and improving its reliability.

[0193] Furthermore, the instantaneous load failure rate analysis results in Tables 8-2 and 9-2 show that since the instantaneous load failure rate of the ceramic electronic components in Examples 45 to 50 and the simulated samples of the low-temperature co-fired ceramic circuit boards in Examples 51 to 53 are all 0%, it can be proven that the ceramic electronic components of this invention can indeed have good current carrying capacity and good reliability.

[0194] Furthermore, since the materials used in this invention for preparing ceramic electronic components do not require cumbersome pre-processing steps (such as, but not limited to, the preparation of glass powder), this invention can be carried out in a simple and efficient manner. Moreover, the materials used in this invention for preparing ceramic electronic components use copper powder instead of conductive powders containing precious metals, thus significantly reducing production costs. Therefore, it is evident that using the materials used in this invention for preparing ceramic electronic components does indeed offer advantages in terms of timeliness and cost, further enhancing the application value of this invention and increasing the diversity and development potential of subsequent product applications.

[0195] The above embodiments are merely examples for the purpose of illustration, and are not intended to limit the scope of the patent application of this invention; any other changes, modifications, or alterations made without departing from the disclosure of this invention should be included in the patent scope covered by this invention.

[0196] 1: Ceramic electronic components 1': Ceramic electronic components 2: Electronic components 3: Solder 10: Ceramic body 10': Ceramic body 101: First end face 101': First end face 102: Second end face 11: Ceramic sublayer 11': Ceramic sublayer 12: Internal electrode 12': Internal electrode 13: Ceramic top cover 14: Ceramic underlayer 20: First terminal electrode 20': First terminal electrode 30: Second terminal electrode 30': Second terminal electrode 40: Solder flux layer 40': Solder flux layer 5B-5B: Section Line C1: Conductive pattern E: Electrode P: Circuit board S1: Dielectric matrix S2:Substrate TH: Through-hole conductor

Claims

1. A ceramic electronic component comprising: a ceramic body having first end faces and second end faces opposite each other; and two first end electrodes; the ceramic body comprising: a plurality of ceramic sublayers and a plurality of internal electrodes; wherein, The ceramic sublayers and the internal electrode system are alternately stacked within the ceramic body; the two first end electrodes respectively cover the first end face and the second end face of the ceramic body and are electrically connected to the internal electrodes; wherein, the ceramic electronic component is made from a raw material composition comprising composition (A) and composition (B); composition (A) comprises: a main powder material and a glass material; the total weight of the main powder material and the glass material is 100 parts by weight, and the content of the glass material is 5 to 20 parts by weight; the main powder material comprises barium titanate microwave dielectric oxide, calcium zirconate microwave dielectric oxide or a combination thereof; wherein, after the glass material undergoes a sintering process at 880°C, its contact angle with the Cu / CuaO substrate is not greater than 20°, α=1 or 2; composition (B) comprises: copper powder, resin, and electrode paste solvent, and based on the total weight of composition (B), composition (B) contains no more than 3% by weight of glass material; The ceramic sublayers of the ceramic body are formed by the composition (A), and the two first end electrodes are formed by the composition (B).

2. The ceramic electronic component as described in claim 1, wherein, The composition (B) does not contain glass material.

3. The ceramic electronic component as described in claim 1, wherein, The barium titanate microwave dielectric oxide in composition (A) comprises: BaTixO2x+1, wherein x = 3.5 to 5.0; the glass material in composition (A) comprises: BaO-ZnO-B2O3-CaO-Al2O3-SiO2-Bi2O3-Cu2O, Na2O-CaO-BaO-ZnO-B2O3-SiO2-Cu2O, or a combination thereof.

4. The ceramic electronic component as described in claim 3, wherein, The composition (A) further comprises a dopant selected from at least one of the group consisting of MnCO3, CaCO3, SrCO3, ZrO2, Dy2O3, and BaWO4.

5. The ceramic electronic component as described in claim 4, wherein, Based on the mole number of the main powder material, the content of the dopant is from 0.45 mole percent to 7.5 mole percent.

6. The ceramic electronic component as described in claim 1, wherein, The calcium zirconate-based microwave dielectric oxide in composition (A) comprises: (SraCa1-a)(Zr1-bMnb)O3, wherein 0 ≤ a < 0.2; 0 ≤ b < 0.3; the glass material in composition (A) comprises: MnO-MgO-Al2O3-SiO2-Cu2O, Li2O-MnO-MgO-Al2O3-SiO2-Cu2O, or a combination thereof.

7. The ceramic electronic component as described in claim 1, wherein, The composition (B) is dried at 120°C to form a green embryo with a green embryo density of 3.5 g / cm³ to 5.8 g / cm³.

8. The ceramic electronic component as described in claim 1, wherein, In the composition (B), the weight ratio of the copper powder to the resin is 25:1 to 6:

1.

9. The ceramic electronic component as described in claim 8, wherein, In the composition (B), the average particle size of the copper powder is 0.1 micrometers to 12 micrometers.

10. A ceramic electronic component as described in any one of claims 1 to 9, wherein, In the ceramic body, two adjacent inner electrodes are respectively connected to the first end face and the second end face of the ceramic body; the inner electrodes contain a base metal.

11. The ceramic electronic component as described in any one of claims 1 to 9, wherein, In the ceramic body, each internal electrode is connected to the first end face and the second end face of the ceramic body; the internal electrodes contain a base metal.

12. The ceramic electronic component as described in any one of claims 1 to 9, wherein, The ceramic electronic component also includes two second terminal electrodes, which are respectively formed on the outer surface of the two first terminal electrodes; wherein the two second terminal electrodes contain nickel.

13. The ceramic electronic component as described in claim 10, wherein, The ceramic electronic component further includes two second terminal electrodes, which are respectively formed on the outer surface of the two first terminal electrodes; wherein the two second terminal electrodes contain nickel.

14. The ceramic electronic component as described in claim 11, wherein, The ceramic electronic component further includes two second terminal electrodes, which are respectively formed on the outer surface of the two first terminal electrodes; wherein the two second terminal electrodes contain nickel.

15. The ceramic electronic component as described in claim 13, wherein, The ceramic electronic component also includes two solder layers, which are respectively formed on the outer surfaces of the two second terminal electrodes; wherein the two solder layers contain tin.

16. The ceramic electronic component as described in claim 14, wherein, The ceramic electronic component also includes two solder layers, which are respectively formed on the outer surfaces of the two second terminal electrodes; wherein the two solder layers contain tin.

17. A ceramic electronic component as described in any one of claims 1 to 9, wherein, This ceramic electronic component is used in embedded ceramic electronic components or surface-mount ceramic electronic components.

18. The ceramic electronic component as described in claim 15, wherein, This ceramic electronic component is applied to surface-mount ceramic electronic components.

19. A ceramic electronic component comprising: a ceramic body having a first end face; two first end electrodes disposed on the first end face of the ceramic body; and two conductor connectors, each of the two conductor connectors disposed in the ceramic body and respectively contacting the two first end electrodes; the ceramic body comprising: a plurality of ceramic sublayers and a plurality of internal electrodes; wherein, The ceramic sublayers and the internal electrode systems are alternately stacked within the ceramic body; each internal electrode is connected to the two conductor connectors, and the internal electrodes are electrically connected to the two first terminal electrodes; wherein the ceramic electronic component is made from a raw material composition comprising composition (A) and composition (B); composition (A) comprises: a main powder material and a glass material; the total weight of the main powder material and the glass material is 100 parts by weight, and the content of the glass material is 5 to 20 parts by weight; the main powder material comprises barium titanate microwave dielectric oxide, calcium zirconate microwave dielectric oxide, or a combination thereof; wherein, after the glass material undergoes a sintering process at 880°C, its contact angle with the Cu / CuaO substrate is not greater than 20°, α=1 or 2; composition (B) comprises: copper powder, resin, and electrode paste solvent, and based on the total weight of composition (B), composition (B) contains no more than 3% by weight of glass material; The ceramic sublayers of the ceramic body are formed by the composition (A), and the two first end electrodes are formed by the composition (B).

20. The ceramic electronic component as described in claim 19, wherein, The composition (B) does not contain glass material.

21. The ceramic electronic component as described in claim 19, wherein, The barium titanate microwave dielectric oxide in composition (A) comprises: BaTixO2x+1, wherein x = 3.5 to 5.0; the glass material in composition (A) comprises: BaO-ZnO-B2O3-CaO-Al2O3-SiO2-Bi2O3-Cu2O, Na2O-CaO-BaO-ZnO-B2O3-SiO2-Cu2O, or a combination thereof.

22. The ceramic electronic component as described in claim 21, wherein, The composition (A) further comprises a dopant selected from at least one of the group consisting of MnCO3, CaCO3, SrCO3, ZrO2, Dy2O3, and BaWO4.

23. The ceramic electronic component as described in claim 22, wherein, Based on the mole number of the main powder material, the content of the dopant is from 0.45 mole percent to 7.5 mole percent.

24. The ceramic electronic component as described in claim 19, wherein, The calcium zirconate-based microwave dielectric oxide in composition (A) comprises: (SraCa1-a)(Zr1-bMnb)O3, wherein 0 ≤ a < 0.2; 0 ≤ b < 0.3; the glass material in composition (A) comprises: MnO-MgO-Al2O3-SiO2-Cu2O, Li2O-MnO-MgO-Al2O3-SiO2-Cu2O, or a combination thereof.

25. The ceramic electronic component as described in claim 19, wherein, The composition (B) is dried at 120°C to form a green embryo with a green embryo density of 3.5 g / cm³ to 5.8 g / cm³.

26. The ceramic electronic component as described in claim 19, wherein, In the composition (B), the weight ratio of the copper powder to the resin is 25:1 to 6:

1.

27. The ceramic electronic component as described in claim 19, wherein, The ceramic electronic component further includes two second terminal electrodes and two flux layers; the two second terminal electrodes are respectively formed on the outer surface of the two first terminal electrodes; wherein the two second terminal electrodes contain nickel; the two flux layers are respectively formed on the outer surface of the two second terminal electrodes; wherein the two flux layers contain tin.

28. A circuit board comprising ceramic electronic components as described in any one of claims 1 to 11, 17, 19 to 26.

29. The circuit board as described in claim 28, wherein, The circuit board also includes a dielectric substrate in which the ceramic electronic component is embedded; the dielectric substrate includes a conductive pattern and a plurality of through-hole conductors, and the ceramic electronic component is connected to the conductive pattern of the dielectric substrate via the through-hole conductors.

30. A circuit board comprising ceramic electronic components as described in any one of claims 12 to 14, 18.

31. A circuit board comprising ceramic electronic components as described in any one of claims 15, 16, and 27.

32. The circuit board as described in claim 31, wherein, The circuit board also includes a substrate with electrodes; the two solder layers in the ceramic electronic component are connected to the electrodes of the substrate.

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