Ceramic electronic component

Abstract

A ceramic electronic component that includes a ceramic insulator and a terminal electrode on a surface of the ceramic insulator. The ceramic insulator contains a crystalline material and an amorphous material. The terminal electrode contains a metal and an oxide. The crystalline material and the oxide contain, in common, at least one type of a metal element. An adjacent region in the ceramic insulator which surrounds the terminal electrode and has a thickness of 5 μm is higher in concentration of the metal element than a remote region which is distant from the terminal electrode by 100 μm and has a thickness of 5 μm.

Claims

1. A ceramic electronic component comprising: a ceramic insulator containing a crystalline material and an amorphous material; and a terminal electrode on a surface of the ceramic insulator, the terminal electrode containing a metal and an oxide, the crystalline material and the oxide containing in common at least one type of a metal element, and in the ceramic insulator, an adjacent region which surrounds the terminal electrode and has a thickness of 5 μm measured as extending outwardly from a border between the terminal electrode and the ceramic insulator is higher in concentration of the metal element than a remote region which is distant from the border between the terminal electrode and the ceramic insulator by 100 μm and has a thickness of 5 μm.

2. The ceramic electronic component according to claim 1, wherein an absolute value of a difference in basicity between the amorphous material and the oxide is not greater than 0.049 when a basicity B of the oxide is calculated as follows: $\begin{array}{cc}B=\underset{i}{.Math.}{n}_{i}B\left(\mathrm{Mi}-O\right)& \left(1\right)\\ B\left(\mathrm{Mi}-O\right)=\frac{B\left(\mathrm{Mi}-O_0\right)-B\left(\mathrm{Si}-O_0\right)}{B\left(\mathrm{Ca}-O_0\right)-B\left(\mathrm{Si}-O_0\right)}& \left(2\right)\\ B\left(\mathrm{Mi}-O_0\right)=\frac{{\left(r_{\mathrm{Mi}}+1.4\right)}^2}{2Z_{\mathrm{Mi}}}& \left(3\right)\end{array}$ where B(Mi-O) is a basicity of each oxide in the terminal electrode, Mi is a cation, MiO is an oxide, B(Mi-O.sub.0) is an oxygen donation capability of MiO, B(Si—O.sub.0) is an oxygen donation capability of SiO.sub.2, B(Ca—O.sub.0) is an oxygen donation capability of CaO, n.sub.i is a composition ratio of each cation Mi, r.sub.Mi is an ion radius (Å) according to Pauling of each cation Mi, and Z.sub.Mi is a valence of each cation Mi.

3. The ceramic electronic component according to claim 1, wherein the adjacent region contains the crystalline material composed of the metal element.

4. The ceramic electronic component according to claim 3, wherein the crystalline material and the oxide contain Ti in common as the metal element.

5. The ceramic electronic component according to claim 4, wherein the crystalline material composed of the metal element contains a fresnoite compound containing Ba, Ti, and Si.

6. The ceramic electronic component according to claim 3, wherein the crystalline material and the oxide contain Al in common as the metal element.

7. The ceramic electronic component according to claim 6, wherein the crystalline material composed of the metal element contains a celsian compound containing Ba, Al, and Si.

8. The ceramic electronic component according to claim 3, wherein the amorphous material contains Ba and Si, and the crystalline material composed of the metal element contains an Si oxide, a fresnoite compound containing Ba, Ti, and Si, and a celsian compound containing Ba, Al, and Si.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1A is a diagram schematically showing as being enlarged, a part of an upper surface and a part of a cross-section of a ceramic electronic component (ceramic wiring board) 100 according to a first embodiment of this invention.

(2) FIG. 1B is a diagram schematically showing as being enlarged, a part of the cross-section of ceramic electronic component 100 at a cut plane including the line X-X shown in FIG. 1A.

(3) FIG. 2 is a diagram schematically showing a green sheet 5 prepared in a first step (green sheet obtaining step) for illustrating one example of a method of manufacturing an evaluation-purpose ceramic electronic component (ceramic wiring board) 100A.

(4) FIG. 3 is a diagram similarly schematically showing green sheet 5 having yet-to-be-fired terminal electrodes 6a to 6e of various sizes formed in a third step (yet-to-be-fired terminal electrode forming step) with a conductor paste obtained in a second step (conductor paste obtaining step).

(5) FIG. 4 is a diagram similarly schematically showing a process of layering green sheets 5 including the green sheet having yet-to-be-fired terminal electrodes 6a to 6e formed in a fourth step (green sheet layering step).

(6) FIG. 5 is a diagram similarly schematically showing a yet-to-be-fired ceramic electronic component 10A obtained in the fourth step (green sheet layering step).

(7) FIG. 6 is a diagram similarly schematically showing evaluation-purpose ceramic electronic component 100A obtained in a fifth step (firing step).

(8) FIG. 7 is a diagram similarly schematically showing a process of layering shrinkage suppression green sheets 8 and green sheets 5 including the green sheet having yet-to-be-fired terminal electrodes 6a to 6e formed in the fourth step further including a shrinkage suppression green sheet layering step.

(9) FIG. 8 is a diagram similarly schematically showing a yet-to-be-fired ceramic electronic component 10B lying between shrinkage suppression green sheets 8 obtained in the fourth step further including the shrinkage suppression green sheet layering step.

(10) FIG. 9 is a diagram similarly schematically showing an evaluation-purpose ceramic electronic component 100B lying between shrinkage suppression green sheets 8 obtained in the fifth step (firing step).

(11) FIG. 10A is a perspective view of a ceramic electronic component (chip type ceramic electronic component) 200 according to a second embodiment of this invention.

(12) FIG. 10B is a side view of ceramic electronic component (chip type ceramic electronic component) 200 according to the second embodiment of this invention.

(13) FIG. 11 is a diagram schematically showing a cross-section of a ceramic wiring board 300 according to the background art.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(14) Features of this invention will be described below in further detail with reference to embodiments of this invention.

(15) <<First Embodiment of Ceramic Electronic Component>>

(16) A ceramic electronic component 100 according to an embodiment of this invention will be described with reference to FIGS. 1A and 1B. In a first embodiment, ceramic electronic component 100 is configured as a ceramic wiring board for mounting active components such as an IC chip and passive components such as a capacitor and interconnecting and modularizing those components.

(17) FIG. 1A is a diagram schematically showing and enlarged, a part of an upper surface of ceramic electronic component 100. FIG. 1B is a diagram schematically showing and enlarged, a part of a cross-section of ceramic electronic component 100 at a cut plane including the line X-X shown in FIG. 1A.

(18) Ceramic electronic component 100 includes a ceramic insulator 1 and a terminal electrode 2. In this embodiment, ceramic insulator 1 contains SiO.sub.2, Al.sub.2O.sub.3, celsian (BaAl.sub.2Si.sub.2O.sub.8), and fresnoite (Ba.sub.2TiSi.sub.2O.sub.8) as a crystalline material which will be described later. The ceramic insulator 1 also contains a glass component containing an oxide of Si, Ba, Mn, Al, Ti, Zr, and Mg as an amorphous material. Terminal electrode 2 contains Cu as a metal as will be described later, and contains TiO.sub.2 and Al.sub.2O.sub.3 as an oxide. A shape of the terminal electrode 2 is rectangular in a top view thereof. Therefore, in the first embodiment, the crystalline material in ceramic insulator 1 and the oxide in terminal electrode 2 contain Ti or Al in common.

(19) As shown in FIGS. 1A and 1B, a region in ceramic insulator 1 having a thickness of 5 μm from a boundary BD between ceramic insulator 1 and terminal electrode 2 is defined as an adjacent region 3. A region having a thickness of 5 μm distant by 100 μm from the boundary BD is defined as a remote region 4 (i.e., a region from 100 μm to 105 μm from the boundary BD is the remote region).

(20) Boundary BD between ceramic insulator 1 and terminal electrode 2, adjacent region 3 surrounding terminal electrode 2 in ceramic insulator 1, and remote region 4 distant from the terminal electrode by a prescribed distance or more are defined with a method below.

(21) Initially, ceramic electronic component 100 is polished with a mechanical polisher to a surface including an axis of symmetry (corresponding to the line X-X in FIG. 1B) in the top view of terminal electrode 2 to thereby expose a cross-section of ceramic electronic component 100. This cross-section is then subjected to flat milling treatment. After carbon coating treatment, element analysis is conducted with a wavelength dispersive X-ray (WDX) spectrometer (trademark JXA-8100 manufactured by JEOL Ltd.). Table 1 shows conditions for measurement with WDX.

(22) TABLE-US-00001 TABLE 1 Apparatus Condition Electronic Probe Current 1 × 10.sup.−7 A Optical Acceleration Voltage 15 KV System Scanning Method Stage Scanning (One Direction) Dwell Time 50 ms The Number of Pixels 250 × 250 Pixel Size 0.6 μm Spectroscope Measurement X-Ray Cu—Kα Dispersive Crystal LiFH

(23) Intensity of Cu in the measurement results with WDX is subjected to ASCII conversion, and a site where a value for intensity of Cu is smaller than 400 is defined as boundary BD between ceramic insulator 1 and terminal electrode 2. In this embodiment, as will be described later, five types of terminal electrodes 2a to 2e in a square shape having lengths of one side of 30 μm, 50 μm, 100 μm, 1 mm, and 2 mm, respectively, are formed as evaluation-purpose ceramic electronic components 100A. In each terminal electrode, an interval between opposing sides is defined as an interval between two boundaries BD under the definition above.

(24) In ceramic insulator 1, adjacent region 3 is higher in concentration of Ti or Al than remote region 4. The hatched portion in FIGS. 1A and 1B schematically shows that fact for ease of understanding in illustration, and cannot be identified based on a visual appearance of an actual ceramic insulator 1. Though adjacent region 3 is arranged in the hatched portion, that is, within a high-concentration region in FIGS. 1A and 1B, the high-concentration region may be located within adjacent region 3 without being limited to the shape shown in the drawings.

(25) A specific experimental result will be described below for clarification. In the description below, a method of manufacturing a sample used for the experiment, that is, an evaluation-purpose ceramic electronic component 100A, is incorporated as the description of a method of manufacturing ceramic electronic component 100.

(26) <First Step (Green Sheet Obtaining Step)>

(27) A method of manufacturing evaluation-purpose ceramic electronic component 100A will be described with reference to FIGS. 2 to 6. FIG. 2 is a diagram schematically showing a green sheet 5 prepared in a first step (green sheet obtaining step).

(28) A method of manufacturing green sheet 5 will be described. Powders of each of SiO.sub.2, Al.sub.2O.sub.3, BaCO.sub.3, ZrO.sub.2, TiO.sub.2, Mg(OH).sub.2, and MnCO.sub.3 having a particle size not greater than 2.0 μm are prepared as starting source materials. The starting source material powders are weighed to achieve a prescribed composition ratio, mixed with a wet method and crushed, and thereafter dried to obtain a mixture. Source material powders for green sheet 5 of a ceramic insulator are obtained by subjecting the obtained mixture to heat treatment for a prescribed time period (for example, within a range from 30 minutes to 300 minutes) at a prescribed temperature (for example, a range from 700° C. to 900° C.) in a reducing atmosphere. As a result of the heat treatment, BaCO.sub.3 is converted to BaO, Mg(OH).sub.2 is converted to MgO, and MnCO.sub.3 is converted to MnO.

(29) Then, ceramic slurry is obtained by adding an organic binder, a dispersant, and a plasticizer to the source material powders for green sheet 5 and mixing and crushing the powders such that the source material powders have an average particle size (D.sub.50) not greater than 1.5 μm. Then, green sheet 5 of which thickness after firing is adjusted to 20 μm is obtained by forming the ceramic slurry into a sheet on a substrate film with a doctor blade method followed by drying.

(30) Using green sheet 5, a sintering start temperature T.sub.1 (° C.) of a yet-to-be-fired ceramic insulator 7 (see FIG. 5) which will be described later and a ratio of shrinkage of a yet-to-be-fired ceramic electronic component 10A (see FIG. 5) in the direction of the main surface are determined. A type of a crystalline material generated after sintering of yet-to-be-fired ceramic insulator 7 is identified.

(31) A method of measuring sintering start temperature T.sub.1 (° C.) of yet-to-be-fired ceramic insulator 7 will be described. A sample for measuring a sintering start temperature of yet-to-be-fired ceramic insulator 7 is obtained by compression bonding ten green sheets 5. Then, a temperature of the sample is increased from a room temperature to 1000° C. at a rate of temperature increase of 2° C./minute with a thermo-mechanical analysis (TMA) apparatus (manufactured by the applicant company) controlled to achieve an atmosphere of N.sub.2/H.sub.2O/H.sub.2 in which Cu is not oxidized.

(32) In results of measurement with TMA, a ratio of shrinkage (%) in a direction of thickness is defined as [(t.sub.1−t.sub.0)/t.sub.0]×100 where an initial thickness is denoted as to and a thickness at a certain temperature is denoted as t.sub.1. A time point when the ratio of shrinkage in the direction of thickness attains to −10% is defined as the sintering start temperature. Consequently, sintering start temperature T.sub.1 of yet-to-be-fired ceramic insulator 7 in the embodiment is 900° C.

(33) A method of determining a ratio of shrinkage of yet-to-be-fired ceramic electronic component 10A in the direction of the main surface will be described. A sample for measuring a ratio of shrinkage of yet-to-be-fired ceramic electronic component 10A in the direction of the main surface is obtained by compression bonding green sheets 5 as many as above. A temperature of this sample is increased from a room temperature to a prescribed temperature (for example, a range from 900° C. to 1000° C.) at a prescribed rate of temperature increase (for example, within a range from 1° C./minute to 5° C./minute) with a firing furnace (manufactured by the applicant company) controlled to achieve an atmosphere where Cu is not oxidized (for example, an N.sub.2H.sub.2O/H.sub.2 atmosphere), and the sample is held at that temperature for a prescribed time period (for example, a range from 60 minutes to 300 minutes) and thereafter cooled to the room temperature.

(34) A ratio of shrinkage (%) of the sample in the direction of the main surface is defined as [(L.sub.1−L.sub.0)/L.sub.0]×100 where a peripheral length of the yet-to-be-fired sample is denoted as L.sub.0 and a peripheral length of the fired sample is denoted as L.sub.1, and the ratio of shrinkage of the sample in the direction of the main surface is calculated. Consequently, the ratio of shrinkage in the direction of the main surface of yet-to-be-fired ceramic electronic component 10A in the embodiment is −5%.

(35) Identification of a type of a crystalline material generated after sintering of yet-to-be-fired ceramic insulator 7 will now be described. A sample for identification of a type of a crystalline material is obtained by subjecting green sheets 5 which are cut in a similar shape to thermal compression bonding under the same conditions as above. A temperature of the sample is increased from a room temperature to a prescribed temperature (for example, a range from 900° C. to 1000° C.) at a prescribed rate of temperature increase (for example, within a range from 1° C./minute to 5° C./minute) with a firing furnace (manufactured by the applicant company) controlled to achieve an atmosphere where Cu is not oxidized (for example, an N.sub.2/H.sub.2O/H.sub.2 atmosphere), and the sample is held at that temperature for a prescribed time period (for example, a range from 60 minutes to 300 minutes) and thereafter cooled to the room temperature. The fired sample is crushed into a powder.

(36) The powder sample is subjected to X-ray diffraction with a diffractometer with Cu-Kα rays used as measurement X-rays. Consequently, the crystalline material generated after sintering of yet-to-be-fired ceramic insulator 7 in the embodiment is identified as SiO.sub.2, Al.sub.2O.sub.3, celsian, and fresnoite.

(37) <Second Step (Conductor Paste Obtaining Step)>

(38) Obtaining a conductor paste to be used for forming yet-to-be-fired terminal electrodes 6a to 6e on green sheet 5 in a third step (yet-to-be-fired terminal electrode forming step which will be described later) will now be described. Metal powders shown in Table 2, oxide powders shown in Table 3, an organic compound shown in Table 4, and an organic vehicle containing an ethyl cellulose resin are prepared as starting source materials.

(39) TABLE-US-00002 TABLE 2 Metal Powder Type Number Type D.sub.50 (μm) True Specific Gravity K-1 Cu 1.5 8.87

(40) TABLE-US-00003 TABLE 3 Oxide Powder True Type Specific SSA Number Type Gravity (m.sup.2/g) Al-1 TiO.sub.2 3.7 5 Al-2 TiO.sub.2 3.7 10 Al-3 TiO.sub.2 3.7 30 Al-4 TiO.sub.2 3.7 90 Al-5 Al.sub.2O.sub.3 3.9 10 * Al-6 SiO.sub.2 2.6 10 * Al-7 Mn.sub.3O.sub.4 4.9 10 * Al-8 ZrO.sub.2 5.8 10 * indicates being out of the range of this invention.

(41) TABLE-US-00004 TABLE 4 Organic True Compound Metal Content* Specific Type Number Type (wt %) Gravity AO-1 Organic Titanium Compound 10 0.95 AO-2 Organic Aluminum 10 0.95 Compound *Percentage with mass of organic compound being defined as denominator and mass of contained metal being defined as numerator

(42) D.sub.50 in Table 2 is measured with a laser diffraction/scattering particle size distribution analyzer (LA series manufactured by Horiba Ltd.) A mixture of ethyl alcohol and isopropyl alcohol is employed as a measurement solvent. A specific surface area (SSA) in Tables 3 and 4 is measured with an SSA measurement apparatus (a trademark Macsorb® manufactured by Mountech Co., Ltd.) with the Brunauer, Emmet and Teller's equation (BET) single-point method with the use of N.sub.2 gas.

(43) A true specific gravity in Tables 2 and 3 is measured with a dry automatic density meter (a trademark Acupic® series manufactured by Shimadzu Corporation) with the use of He gas, and a true specific gravity in Table 4 is measured with a specific gravity cup (manufactured by Yasuda Seiki Seisakusho, Ltd.). A metal content in Table 4 is measured with an inductively coupled plasma atomic emission spectrometer (ICP-AES manufactured by Shimadzu Corporation).

(44) Conductor pastes labeled with conductor paste composition numbers P-1 to P-18 are obtained by blending starting source materials shown in Tables 2 to 4 to achieve a composition ratio shown in Table 5 and dispersing the starting source materials with a triple roll mill.

(45) TABLE-US-00005 TABLE 5 Composition (Vol %) Additive Conductor Paste Organic Composition Metal Powders Oxide Powders Compound Number K-1 AI-1 AI-2 AI-3 AI-4 AI-5 AI-6 AI-7 AI-8 AO-1 AO-2 Organic Vehicle P-1 39.2 — 0.8 — — — — — — — — 60.0 P-2 38.4 — 1.6 — — — — — — — — 60.0 P-3 36.0 — 4.0 — — — — — — — — 60.0 P-4 34.0 — 6.0 — — — — — — — — 60.0 P-5 36.8 3.2 — — — — — — — — — 60.0 P-6 39.2 — — 0.8 — — — — — — — 60.0 P-7 39.6 — — — 0.4 — — — — — — 60.0 P-8 38.4 — — — — 1.6 — — — — — 60.0 P-9 34.0 — — — — 6.0 — — — — — 60.0 * P-10 38.4 — — — — — 1.6 — — — — 60.0 * P-11 34.0 — — — — — 6.0 — — — — 60.0 * P-12 38.4 — — — — — — 1.6 — — — 60.0 * P-13 34.0 — — — — — — 6.0 — — — 60.0 * P-14 38.4 — — — — — — — 1.6 — — 60.0 * P-15 34.0 — — — — — — — 6.0 — — 60.0 * P-16 40.0 — — — — — — — — — — 60.0 P-17 38.4 — — — — — — — — 16.0 — 45.6 P-18 38.4 — — — — — — — — — 16.0 45.6 * indicates being out of the range of this invention.

(46) <Third Step (Yet-To-Be-Fired Terminal Electrode Forming Step)>

(47) FIG. 3 is a diagram schematically showing green sheet 5 having yet-to-be-fired terminal electrodes 6a to 6e formed in a third step (yet-to-be-fired terminal electrode forming step). Yet-to-be-fired terminal electrodes 6a to 6e are formed in a square shape having lengths of one side of 30 μm, 50 μm, 100 μM, 1 mm, and 2 mm, respectively, after firing as described previously. One hundred pieces of each of yet-to-be-fired terminal electrodes 6a to 6e are formed on one green sheet such that an interval thereamong after firing is set to 500 μm.

(48) Green sheet 5 shown in FIG. 3 is obtained by printing on green sheet 5, the conductor paste obtained in the second step (conductor paste obtaining step) into a shape shown in FIG. 3 with a screen printing method.

(49) <Fourth Step (Green Sheet Layering Step)>

(50) FIG. 4 is a diagram schematically showing a process of layering green sheets 5 including the green sheet having yet-to-be-fired terminal electrodes 6a to 6e formed in a fourth step (green sheet layering step). At this time, a prescribed number of green sheets are layered such that yet-to-be-fired terminal electrodes 6a to 6e do not lie between green sheets 5, that is, yet-to-be-fired terminal electrodes 6a to 6e are arranged at the top as shown in FIG. 4.

(51) FIG. 5 is a diagram similarly schematically showing yet-to-be-fired ceramic electronic component 10A obtained in the fourth step (green sheet layering step). Yet-to-be-fired ceramic electronic component 10A is obtained by compression bonding green sheets 5 layered as above and including the green sheet having yet-to-be-fired terminal electrodes 6a to 6e formed. Yet-to-be-fired ceramic electronic component 10A includes yet-to-be-fired ceramic insulator 7 and yet-to-be-tired terminal electrodes 6a to 6e.

(52) <Fifth Step (Firing Step)>

(53) A firing step of obtaining evaluation-purpose ceramic electronic component 100A by firing yet-to-be-fired ceramic electronic component 10A obtained in the fourth step will be described. The step of firing yet-to-be-fired ceramic electronic component 10A includes four sub steps below.

(54) A raw multilayer body is subjected to heat treatment under a prescribed condition in a reducing atmosphere in order to decompose an organic binder contained in yet-to-be-fired ceramic insulator 7 and yet-to-be-fired terminal electrodes 6a to 6e (a first sub step). When yet-to-be-fired terminal electrodes 6a to 6e contain an organic compound containing a metal (conductor paste composition numbers P-17 and P-18), the organic compound is converted to a metal oxide through this step.

(55) After the first sub step, heat treatment under a prescribed condition in a reducing atmosphere is performed such that remaining C contained in yet-to-be-fired ceramic electronic component 10A is lower than 0.1 wt % (a second sub step).

(56) After the second sub step, heat treatment under a prescribed condition in a reducing atmosphere is performed. In this step, yet-to-be-fired ceramic insulator 7 is converted to ceramic insulator 1 comprising a glass ceramic containing a crystalline material and an amorphous material. Yet-to-be-fired terminal electrodes 6a to 6e are converted to terminal electrodes 2a to 2e. A product resulting from partial reduction of an oxide contained in yet-to-be-fired terminal electrodes 6a to 6e through burning of remaining C in the second sub step is sufficiently oxidized again (a third sub step).

(57) After the third sub step, in order to diffuse the oxide in terminal electrodes 2a to 2e into the amorphous material in ceramic insulator 1, heat treatment under a prescribed condition in a reducing atmosphere is performed (a fourth sub step). After the glass ceramic forming step, a temperature is increased at a rate of temperature increase of 2° C./minute up to 980° C. higher by 80° C. than sintering start temperature T.sub.1 of yet-to-be-fired ceramic insulator 7, and the temperature is held for two hours. At this time, by controlling a flow rate of N.sub.2/H.sub.2/H.sub.2O/O.sub.2, an atmosphere is controlled to an atmosphere in which Cu is reduced but the oxide contained in yet-to-be-fired terminal electrodes 6a to 6e maintains the oxidized state. In this step, the oxide in terminal electrodes 2a to 2e is diffused into the amorphous material in ceramic insulator 1. Consequently, a concentration in the adjacent region surrounding terminal electrodes 2a to 2e, of the metal element contained in common in the crystalline material in ceramic insulator 1 and terminal electrodes 2a to 2e is higher than a concentration thereof in remote region 4.

(58) FIG. 6 is a diagram schematically showing evaluation-purpose ceramic electronic component 100A including ceramic insulator 1 and terminal electrodes 2a to 2e obtained in the step above. FIG. 6 does not show the adjacent region.

(59) A type of the crystalline material in ceramic insulator 1 of evaluation-purpose ceramic electronic component 100A obtained as above is identified, a composition of the amorphous material therein is analyzed, and a basicity of the amorphous material therein is calculated. Table 6 shows results thereof. Analytical specimen numbers (S-1 to S-18) corresponding to types of the conductor paste are allocated to evaluation-purpose ceramic electronic components 100A subjected to various types of evaluation.

(60) TABLE-US-00006 TABLE 6 Composition of Glass Ceramic in Portion Distant by 250 μm from Terminal Electrode Analytical Amorphous Oxide Specimen Crystalline Oxide Composition (mol %) Number Conductor Paste Type SiO.sub.2 BaO MnO Al.sub.2O.sub.3 TiO.sub.2 ZrO.sub.2 MgO Basicity S-1 P-1 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 S-2 P-2 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 S-3 P-3 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 S-4 P-4 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 S-5 P-5 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 S-6 P-6 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 S-7 P-7 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 S-8 P-8 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 S-9 P-9 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 * S-10 P-10 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 * S-11 P-11 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 * S-12 P-12 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 * S-13 P-13 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 * S-14 P-14 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 * S-15 P-15 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 * S-16 P-16 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 S-17 P-17 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 S-18 P-18 SiO.sub.2, Al.sub.2O.sub.3, BaAl.sub.2Si.sub.2O.sub.8, Ba.sub.2TiSi.sub.2O.sub.8 82.89 6.96 3.34 2.41 2.06 1.32 1.02 0.1427 * indicates being out of the range of this invention.

(61) A method of identifying a type of the crystalline material in ceramic insulator 1 will be described. Initially, evaluation-purpose ceramic electronic component 100A is polished with a mechanical polisher to a surface including an axis of symmetry (corresponding to the line Y-Y in FIG. 3) in the top view of terminal electrode 2 to thereby expose a cross-section of evaluation-purpose ceramic electronic component 100A. This cross-section is then subjected to flat milling treatment. A thin piece is obtained by subjecting a portion in the cross-section of evaluation-purpose ceramic electronic component 100A which is distant by 100 μm from boundary BD between ceramic insulator 1 and terminal electrodes 2a to 2e defined as described previously to focused ion beam (FIB) processing.

(62) The obtained thin piece is analyzed with a scanning transmission electron microscope (STEM/a trademark HD-2300A manufactured by Hitachi Ltd.) and energy dispersive analysis of X-ray (EDAX/a trademark Genesis XM4 manufactured by AMETEK Inc.) so as to examine presence of the crystalline material. Furthermore, a site identified as the crystalline material is subjected to selected area electron diffraction with the use of a field-emission type transmission electron microscope (FE-TEM/a trademark JEM-2200FS manufactured by JEOL Ltd.) so as to calculate various spacings between crystals based on an obtained diffraction pattern and so as to identify the crystalline material matching with the spacing. Table 7 shows conditions for analysis with STEM/EDAX. Results obtained as above are shown in the field of type of crystalline oxide in Table 6.

(63) TABLE-US-00007 TABLE 7 Apparatus Condition STEM Acceleration Voltage 200 kV Variable Aperture of Objective #2 Probe Diameter Normal Mode Pre-Treatment Pt Coating EDX Time Constant 12.8 μs The Number of Map Integrations 16 Dwell Time 500

(64) A method of analyzing a composition of the amorphous material in ceramic insulator 1 will be described. A thin piece obtained as in identification of a type of the crystalline material is subjected to analysis with EDX with the use of STEM/EDAX so as to analyze the composition of the amorphous material. Results obtained as above are shown in the field of type of amorphous oxide in Table 6.

(65) Basicity B of the amorphous material is calculated in accordance with expressions (1) to (3) below based on the composition of the amorphous material obtained through analysis with EDX. Results obtained as above are shown in the field of basicity in Table 6.

(66) $\begin{array}{cc}B=\underset{i}{.Math.}{n}_{i}B\left(\mathrm{Mi}-O\right)& \left(1\right)\\ B\left(\mathrm{Mi}-O\right)=\frac{B\left(\mathrm{Mi}-O_0\right)-B\left(\mathrm{Si}-O_0\right)}{B\left(\mathrm{Ca}-O_0\right)-B\left(\mathrm{Si}-O_0\right)}& \left(2\right)\\ B\left(\mathrm{Mi}-O_0\right)=\frac{{\left(r_{\mathrm{Mi}}+1.4\right)}^2}{2Z_{\mathrm{Mi}}}& \left(3\right)\end{array}$

(67) In the expressions, B(Mi-O) represents a basicity of each oxide in the terminal electrode (a cation being expressed as Mi), B(Mi-O.sub.0) represents oxygen donation capability of MiO when an oxide of a certain element is expressed as MiO, B(Si—O.sub.0) represents oxygen donation capability of SiO.sub.2, B(Ca—O.sub.0) represents oxygen donation capability of CaO, n.sub.i represents a composition ratio of each cation Mi, r.sub.Mi, represents an ion radius (Å) of each cation Mi, and Z.sub.Mi represents a valence of each cation Mi. B(Mi-O) is calculated by using a value of an ion radius according to Pauling as a value of an ion radius of each cation Mi and obtained by rounding a calculated value off to four decimal places.

(68) Since there is only one type of oxide powder in the terminal electrode as shown in Table 3 in the experimental example herein, a condition of B=B(Mi-O) is satisfied. Alternatively, a plurality of types of oxide powders mixed together may be used. For example, TiO.sub.2 and Al.sub.2O.sub.3 can be mixed and used as oxide powders in the terminal electrode. In that case, a condition of B=n.sub.TiB.sub.Ti-0+n.sub.Al-0B.sub.Al-0 (n.sub.Ti+n.sub.Al=1) is satisfied.

(69) A type of the oxide in terminal electrodes 2a to 2e of evaluation-purpose ceramic electronic component 100A obtained as above is identified and a basicity of the oxide is calculated. Table 8 shows results.

(70) TABLE-US-00008 TABLE 8 Analytical Composition of Crystalline Oxide in Terminal Electrode Specimen Conductor Type Basicity Number Paste 30 μm□ 50 μm□ 100 μm□ 1 mm□ 2 mm□ 30 μm□ 50 μm□ 100 μm□ 1 mm□ 2 mm□ S-1 P-1 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 0.1250 0.1250 0.1250 0.1250 0.1250 S-2 P-2 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 0.1250 0.1250 0.1250 0.1250 0.1250 S-3 P-3 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 0.1250 0.1250 0.1250 0.1250 0.1250 S-4 P-4 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 0.1250 0.1250 0.1250 0.1250 0.1250 S-5 P-5 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 0.1250 0.1250 0.1250 0.1250 0.1250 S-6 P-6 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 0.1250 0.1250 0.1250 0.1250 0.1250 S-7 P-7 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 0.1250 0.1250 0.1250 0.1250 0.1250 S-8 P-8 Al.sub.2O.sub.3 Al.sub.2O.sub.3 Al.sub.2O.sub.3 Al.sub.2O.sub.3 Al.sub.2O.sub.3 0.1913 0.1913 0.1913 0.1913 0.1913 S-9 P-9 Al.sub.2O.sub.3 Al.sub.2O.sub.3 Al.sub.2O.sub.3 Al.sub.2O.sub.3 Al.sub.2O.sub.3 0.1913 0.1913 0.1913 0.1913 0.1913 * S-10 P-10 SiO.sub.2 SiO.sub.2 SiO.sub.2 SiO.sub.2 SiO.sub.2 0 0 0 0 0 * S-11 P-11 SiO.sub.2 SiO.sub.2 SiO.sub.2 SiO.sub.2 SiO.sub.2 0 0 0 0 0 * S-12 P-12 MnO MnO MnO MnO MnO 0.7850 0.7850 0.7850 0.7850 0.7850 * S-13 P-13 MnO MnO MnO MnO MnO 0.7850 0.7850 0.7850 0.7850 0.7850 * S-14 P-14 ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 0.1829 0.1829 0.1829 0.1829 0.1829 * S-15 P-15 ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 0.1829 0.1829 0.1829 0.1829 0.1829 * S-16 P-16 — — — — — — — — — — S-17 P-17 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 TiO.sub.2 0.1250 0.1250 0.1250 0.1250 0.1250 S-18 P-18 Al.sub.2O.sub.3 Al.sub.2O.sub.3 Al.sub.2O.sub.3 Al.sub.2O.sub.3 Al.sub.2O.sub.3 0.1913 0.1913 0.1913 0.1913 0.1913 * indicates being out of the range of this invention.

(71) A method of identifying a type of the oxide in terminal electrodes 2a to 2e will be described. Initially, evaluation-purpose ceramic electronic component 100A is polished with a mechanical polisher to a surface including the axis of symmetry (corresponding to the line Y-Y in FIG. 3) in the top view of terminal electrodes 2a to 2e to thereby expose a cross-section of evaluation-purpose ceramic electronic component 100A. This cross-section is then subjected to flat milling treatment. A region in terminal electrodes 2a to 2e distant by 10 μm or more from the main surface of evaluation-purpose ceramic electronic component 100A in the cross-section of evaluation-purpose ceramic electronic component 100A is formed into a thin piece through FIB processing.

(72) A type of the oxide scattered over the region in the obtained thin piece is identified with a method the same as the method of identifying a type of the crystalline material in ceramic insulator 1 described previously. Consequently, the detected oxide is confirmed as being crystalline and being composed substantially of a single component. Results obtained as above are shown in the field of type of crystalline oxide in terminal electrode in Table 8.

(73) Basicity B of the oxide confirmed above is calculated in accordance with the expressions (1) to (3) described previously. Results obtained above are shown in the field of basicity of crystalline oxide in terminal electrode in Table 8.

(74) Interaction between ceramic insulator 1 and terminal electrodes 2a to 2e is analyzed based on results of analysis of ceramic insulator 1 and terminal electrodes 2a to 2e. Table 9 shows results.

(75) TABLE-US-00009 TABLE 9 Analytical Specimen Conductor Element in Difference in Basicity Number Paste Common 30 μm□ 50 μm□ 100 μm□ 1 mm□ 2 mm□ S-1 P-1 Ti 0.018 0.018 0.018 0.018 0.018 S-2 P-2 Ti 0.018 0.018 0.018 0.018 0.018 S-3 P-3 Ti 0.018 0.018 0.018 0.018 0.018 S-4 P-4 Ti 0.018 0.018 0.018 0.018 0.018 S-5 P-5 Ti 0.018 0.018 0.018 0.018 0.018 S-6 P-6 Ti 0.018 0.018 0.018 0.018 0.018 S-7 P-7 Ti 0.018 0.018 0.018 0.018 0.018 S-8 P-8 Al 0.049 0.049 0.049 0.049 0.049 S-9 P-9 Al 0.049 0.049 0.049 0.049 0.049 * S-10 P-10 Si 0.143 0.143 0.143 0.143 0.143 * S-11 P-11 Si 0.143 0.143 0.143 0.143 0.143 * S-12 P-12 None 0.642 0.642 0.642 0.642 0.642 * S-13 P-13 None 0.642 0.642 0.642 0.642 0.642 * S-14 P-14 None 0.040 0.040 0.040 0.040 0.040 * S-15 P-15 None 0.040 0.040 0.040 0.040 0.040 * S-16 P-16 None — — — — — S-17 P-17 Ti 0.018 0.018 0.018 0.018 0.018 S-18 P-18 Al 0.049 0.049 0.049 0.049 0.049 * indicates being out of the range of this invention.

(76) The metal element contained in common in the amorphous material in ceramic insulator 1 and the oxide in terminal electrodes 2a to 2e is shown in the field of element in common in Table 9. An absolute value of a difference in basicity between the amorphous material in ceramic insulator 1 and the oxide in terminal electrodes 2a to 2e is shown in the field of difference in basicity in Table 9. A difference in basicity is obtained by rounding a calculated value off to three decimal places.

(77) A concentration of the element in common in the adjacent region surrounding terminal electrodes 2a to 2e in ceramic insulator 1 and a concentration of the element in common in the remote region are analyzed. The crystalline material containing the element in common which is present in the adjacent region is identified. Table 10 shows results.

(78) TABLE-US-00010 TABLE 10 Adjacent Region 30 μm□ 50 μm□ 100 μm□ 1 mm□ 2 mm□ Analytical Element Element Element Element Element Specimen Conductor in Crystalline in Com- Crystalline in Com- Crystalline in Com- Crystalline in Com- Crystalline Number Paste Common Oxide mon Oxide mon Oxide mon Oxide mon Oxide S-1 P-1 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 S-2 P-2 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 S-3 P-3 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 S-4 P-4 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 S-5 P-5 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 S-6 P-6 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 S-7 P-7 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 S-8 P-8 ∘ BaAl.sub.2Si.sub.2O.sub.8 ∘ BaAl.sub.2Si.sub.2O.sub.8 ∘ BaAl.sub.2Si.sub.2O.sub.8 ∘ BaAl.sub.2Si.sub.2O.sub.8 ∘ BaAl.sub.2Si.sub.2O.sub.8 S-9 P-9 ∘ BaAl.sub.2Si.sub.2O.sub.8 ∘ BaAl.sub.2Si.sub.2O.sub.8 ∘ BaAl.sub.2Si.sub.2O.sub.8 ∘ BaAl.sub.2Si.sub.2O.sub.8 ∘ BaAl.sub.2Si.sub.2O.sub.8 * S-10 P-10 x — x — x — x — x — * S-11 P-11 x — x — x — x — x — * S-12 P-12 x — x — x — x — x — * S-13 P-13 x — x — x — x — x — * S-14 P-14 x — x — x — x — x — * S-15 P-15 x — x — x — x — x — * S-16 P-16 x Ba.sub.2TiSi.sub.2O.sub.8 x Ba.sub.2TiSi.sub.2O.sub.8 x Ba.sub.2TiSi.sub.2O.sub.8 x Ba.sub.2TiSi.sub.2O.sub.8 x Ba.sub.2TiSi.sub.2O.sub.8 S-17 P-17 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 ∘ Ba.sub.2TiSi.sub.2O.sub.8 S-18 P-18 ∘ BaAl.sub.2Si.sub.2O.sub.8 ∘ BaAl.sub.2Si.sub.2O.sub.8 ∘ BaAl.sub.2Si.sub.2O.sub.8 ∘ BaAl.sub.2Si.sub.2O.sub.8 ∘ BaAl.sub.2Si.sub.2O.sub.8 * indicates being out of the range of this invention.

(79) A method of analyzing a concentration of the element in common in the adjacent region and a concentration of the element in common in the remote region will be described. Initially, evaluation-purpose ceramic electronic component 100A is polished with a mechanical polisher to a surface including the axis of symmetry (corresponding to the line Y-Y in FIG. 3) in the top view of terminal electrodes 2a to 2e to thereby expose a cross-section of evaluation-purpose ceramic electronic component 100A. This cross-section is then subjected to flat milling treatment. After carbon coating treatment, element analysis is conducted with a wavelength dispersive X-ray (WDX) spectrometer (a trademark JXA-8100 manufactured by JEOL Ltd.) to thereby check a concentration of the element in common. Conditions for measurement with WDX are the same as shown in Table 1.

(80) Then, a concentration of the element in common in the adjacent region is compared with a concentration of the element in common in the remote region. When the concentration of the element in common in the adjacent region is higher, a circle is shown in the field of element in common in Table 10. When a concentration of the element in common in the adjacent region is equal to or lower than the concentration of the element in common in the remote region, a cross is shown in the field of element in common in Table 10.

(81) A method of identifying the crystalline material containing the element in common which is present in the adjacent region will be described. A type of the oxide scattered over the adjacent region higher in concentration of the element in common as a result of analysis above is identified with a method the same as the method of identifying a type of the crystalline material in ceramic insulator 1 described previously. Results obtained above are shown in the field of type of crystalline oxide in adjacent region in Table 10.

(82) Adhesion of plating of an outer surface of terminal electrodes 2a to 2e, separation between ceramic insulator 1 and terminal electrodes 2a to 2e, and denseness of terminal electrodes 2a to 2e are evaluated. Table 11 shows results.

(83) TABLE-US-00011 TABLE 11 Analytical Evaluation Result Specimen Conductor Adhesion of Plating Comprehensive Number Paste 30 μm 50 μm 100 μm 1 mm 2 mm Separation Denseness Evaluation S-1 P-1 A A A A A A S A S-2 P-2 S S S S S A S S S-3 P-3 S S S S S A S S S-4 P-4 A A A A A A A A S-5 P-5 S S S S S A S S S-6 P-6 S S S S S A S S S-7 P-7 S S S S S A S S S-8 P-8 A A A A A A S A S-9 P-9 A A A A A A A A * S-10 P-10 B B B B B A S B * S-11 P-11 B B B B B A A B * S-12 P-12 B B B B B A S B * S-13 P-13 B B B B B A A B * S-14 P-14 B B B B B A S B * S-15 P-15 B B B B B A A B S-16 P-16 B A A S S B S B S-17 P-17 S S S S S A S S S-18 P-18 A A A A A A S A * indicates being out of the range of this invention.

(84) A method of evaluating adhesion of plating of terminal electrodes 2a to 2e will be described. Terminal electrodes 2a to 2e are subjected to electroless Ni plating treatment. After the plating treatment, a thickness of Ni plating on the surface of an end portion of each of terminal electrodes 2a to 2e is measured with fluorescent X-rays. The number of samples subjected to measurement is set to one hundred for each of terminal electrodes 2a to 2e.

(85) An average value of thicknesses of Ni platings for each of terminal electrodes 2a to 2e is calculated, and a specimen of which thickness of Ni plating exceeds 4 μm is determined as being particularly good in adhesion of Ni plating and “S” is shown in the field of adhesion of plating in evaluation result in Table 11. A specimen of which thickness of Ni plating is not smaller than 1 μm and not greater than 4 μm is determined as being good in adhesion of Ni plating and “A” is shown in the field in Table 11. A specimen of which thickness of Ni plating is smaller than 1 μm is determined as being poor in adhesion of Ni plating and “B” is shown in the field in Table 11.

(86) A method of evaluating separation between ceramic insulator 1 and terminal electrodes 2a to 2e will be described. Evaluation-purpose ceramic electronic component 100A is immersed in a fluorescent solution. After the treatment for immersion in the fluorescent solution, the evaluation-purpose ceramic electronic component is dried for ten minutes at 150° C. with a hot air drier. Then, evaluation-purpose ceramic electronic component 100A is polished with a mechanical polisher to a surface including the axis of symmetry (corresponding to the line Y-Y in FIG. 3) in the top view of terminal electrodes 2a to 2e to thereby expose a cross-section of evaluation-purpose ceramic electronic component 100A. The cross-section is observed with a fluorescent microscope and whether or not a portion between ceramic insulator 1 and terminal electrodes 2a to 2e is impregnated with the fluorescent solution is observed. The number of measurement samples is set to ten for each of terminal electrodes 2a to 2e.

(87) Among the ten samples for each of terminal electrodes 2a to 2e, specimens none of which is impregnated with the fluorescent solution in the portion between ceramic insulator 1 and each terminal electrode are determined as being free from separation between ceramic insulator 1 and each terminal electrode and “A” is shown in the field of separation in evaluation result in Table 11. Specimens among which even one is found to be impregnated with the fluorescent solution in the portion between ceramic insulator 1 and each terminal electrode are determined as having experienced separation between ceramic insulator 1 and each terminal electrode and “B” is shown in the field in Table 11.

(88) A method of evaluating denseness of terminal electrodes 2a to 2e will be described. A cross-section of evaluation-purpose ceramic electronic component 100A exposed with a method the same as above is observed with a fluorescent microscope and a depth of impregnation with the fluorescent solution into terminal electrodes 2a to 2e is observed. The number of measurement samples is set to ten for each of terminal electrodes 2a to 2e.

(89) An average value of depths of impregnation with the fluorescent solution for each of terminal electrodes 2a to 2e is calculated. A specimen of which depth of impregnation with the fluorescent solution is smaller than 5 μm is determined as being particularly good in denseness and “S” is shown in the field of denseness in evaluation result in Table 11. A specimen of which depth of impregnation with the fluorescent solution is not smaller than 5 μm and not greater than 10 μm is determined as being good in denseness and “A” is shown in the field in Table 11. A specimen of which depth of impregnation with the fluorescent solution exceeds 10 μm is determined as being poor in denseness and “B” is shown in the field in Table 11.

(90) A specimen including even one item evaluated as “B” among three items of adhesion of plating, separation, and denseness evaluated as above is determined as being out of the range of this invention and “B” is shown in the field of comprehensive evaluation in evaluation result in Table 11. A specimen without any item evaluated as “B” among the three items, in which adhesion of plating of terminal electrode 2c (in a square shape having one side of 100 μm) is evaluated as “S”, is determined as being particularly good and “S” is shown in the field in Table 11. A specimen without any item evaluated as “B” among the three items, in which adhesion of plating of terminal electrode 2c is evaluated as “A”, is determined as being good and “A” is shown in the field in Table 11.

(91) As is clear from Table 11, evaluation-purpose ceramic electronic components 100A having analytical specimen numbers S-1 to S-9 and analytical specimen numbers S-17 and S-18 within the range of this invention are excellent in adhesion of plating, separation, and denseness.

(92) As described previously, in ceramic insulator 1 included in evaluation-purpose ceramic electronic component 100A, in firing yet-to-be-fired ceramic electronic component 10A, ions of the metal in common described previously are diffused into the amorphous material in ceramic insulator 1. Since a solid solubility limit of the ions is low, ions of the element in common and the component in the amorphous material react with each other and the crystalline material is precipitated from the amorphous material. Consequently, an amount of the amorphous material contained in ceramic insulator 1 decreases. When the ions of the element in common and the amorphous material react with each other and the amorphous material is converted to the crystalline material, a metal element in the amorphous material (for example, an alkaline-earth metal element) with a function to lower a viscosity of the amorphous material in a molten state at a high temperature is taken into the crystalline material. Therefore, the remaining amorphous material is high in viscosity at a high temperature.

(93) It is considered that, owing to the effect above, in firing yet-to-be-fired ceramic electronic component 10A, the amorphous material introduced into yet-to-be-fired terminal electrodes 6a to 6e from yet-to-be-fired ceramic insulator 7 decreases and covering of the upper surface of terminal electrodes 2a to 2e with the amorphous material is suppressed.

(94) TiO.sub.2 which makes a difference in basicity smaller is smaller than Al.sub.2O.sub.3 in amount of solid solution in the amorphous material in ceramic insulator 1. In addition, when TiO.sub.2 solid solution is formed in the amorphous material in yet-to-be-fired ceramic insulator 7, the crystalline material (fresnoite) is immediately formed. It is consequently estimated that a viscosity of the amorphous material in ceramic insulator 1 in the adjacent region surrounding yet-to-be-fired terminal electrodes 6a to 6e increases and introduction of the amorphous material into yet-to-be-fired terminal electrodes 6a to 6e is blocked.

(95) <Modification of Method of Manufacturing Ceramic Electronic Component>

(96) A modification of the method of manufacturing ceramic electronic component 100 according to the first embodiment of this invention will be described with reference to FIGS. 7 to 9. A modification of the method of manufacturing evaluation-purpose ceramic electronic component 100A is incorporated as the description of the modification of the method of manufacturing ceramic electronic component 100 also in the description below.

(97) In the modification, the first to third steps and the fifth step are the same as in the method of manufacturing evaluation-purpose ceramic electronic component 100A described previously. The fourth step further including a shrinkage suppression green sheet layering step will be described below, and detailed description of other steps will briefly be mentioned.

(98) A shrinkage suppression green sheet 8 containing Al.sub.2O.sub.3 as source material powders for a shrinkage suppression material is obtained with a method the same as the first step in the method of manufacturing evaluation-purpose ceramic electronic component 100A described previously. Through the first to third steps, green sheet 5 having yet-to-be-fired terminal electrodes 6a to 6e of various sizes formed is obtained.

(99) FIG. 7 is a diagram schematically showing a process of layering shrinkage suppression green sheets 8 and green sheets 5 including the green sheet having yet-to-be-fired terminal electrodes 6a to 6e formed when the fourth step (green sheet layering step) described previously further includes the shrinkage suppression green sheet layering step.

(100) A yet-to-be-fired ceramic electronic component 10B is obtained by layering a prescribed number of shrinkage suppression green sheets 8 obtained as above and a prescribed number of green sheets 5 and thermally compression bonding them in the fourth step. Compression bonded yet-to-be-fired ceramic electronic component 10B is set to lie between shrinkage suppression green sheets 8 such that yet-to-be-fired terminal electrodes 6a to 6e do not lie between green sheets 5. Though the number of shrinkage suppression green sheets 8 to be layered is set to any number, the shrinkage suppression green sheets should be layered to such an extent that shrinkage of yet-to-be-fired ceramic electronic component 10B in the direction of the main surface during firing is suppressed.

(101) FIG. 8 is a diagram schematically showing yet-to-be-fired ceramic electronic component 10B lying between shrinkage suppression green sheets 8. Conditions for thermal compression bonding are the same as those in thermal compression bonding of yet-to-be-fired ceramic electronic component 10A. Yet-to-be-fired ceramic electronic component 10B includes yet-to-be-fired ceramic insulator 7, yet-to-be-fired terminal electrodes 6a to 6e, and shrinkage suppression green sheet 8.

(102) Thereafter, an evaluation-purpose ceramic electronic component 100B lying between shrinkage suppression layers 9 shown in FIG. 9 is obtained by firing yet-to-be-fired ceramic electronic component 10B in the fifth step (firing step). Thereafter, the shrinkage suppression layers are removed by sand-blasting evaluation-purpose ceramic electronic component 100B. Evaluation-purpose ceramic electronic component 100A described previously can be obtained as above.

(103) According to the method of manufacturing a ceramic electronic component, shrinkage of ceramic insulator 1 and terminal electrodes 2a to 2e in the direction of the main surface is suppressed as described previously. Therefore, dimension accuracy of the fired ceramic electronic component can extremely be high.

(104) <<Second Embodiment of Ceramic Electronic Component>>

(105) A ceramic electronic component 200 according to an embodiment of this invention will be described with reference to FIGS. 10A and 10B. Ceramic electronic component 100 in the first embodiment is a ceramic electronic component in which a terminal electrode is formed on a surface of a chip type ceramic electronic component body.

(106) FIG. 10A is a perspective view of ceramic electronic component 200. FIG. 10B is a side view of ceramic electronic component 200.

(107) Ceramic electronic component 200 includes ceramic insulator 1 and terminal electrodes 2A to 2F. In ceramic electronic component 200 as well, as in ceramic electronic component 100 described previously, ceramic insulator 1 contains a crystalline material and an amorphous material and terminal electrodes 2A to 2F contain a metal and an oxide. The crystalline material and the oxide contain at least one type of metal element in common. The oxide in terminal electrodes 2A to 2F is diffused during firing, and the adjacent region which surrounds terminal electrodes 2A to 2F and has a thickness of 5 μm is higher in concentration of the metal element than the remote region which is distant from the terminal electrode by 100 μm and has a thickness of 5 μm.

(108) Not only in the ceramic wiring board but also in the chip type ceramic electronic component, covering of the upper surface of terminal electrodes 2A to 2F with the amorphous material is similarly suppressed. Consequently, a plating film can reliably and readily be formed on the upper surface of the terminal electrode. Ions of the metal element which is the component of the oxide in terminal electrodes 2A to 2F are diffused in the amorphous material in the ceramic insulator, so that terminal electrodes 2A to 2F and ceramic insulator 1 are firmly bonded to each other and separation between terminal electrodes 2A to 2F and ceramic insulator 1 is suppressed.

(109) This invention is not limited to the embodiments above and is susceptible to various applications and modifications within the scope of this invention. It is pointed rout that functions described herein are presumed functions and that this invention is not implemented only by these functions. It is also pointed out that each embodiment described herein is illustrative and partial replacement or combination of features in different embodiments can be made.

(110) Though embodiments and modifications of the present invention have been described above, the embodiments and the modifications disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims and includes any modifications within the scope and meaning equivalent to the terms of the claims.

REFERENCE SIGNS LIST

(111) 100, 200 ceramic electronic component; 1 ceramic insulator, 2 terminal electrode; 3 adjacent region; and 4 remote region