# US 10,872,725 B2 · Ceramic dielectric, method of manufacturing the same, ceramic electronic component, and electronic device

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- Number: US 10,872,725 B2
- Document ID: US10872725B2
- Status: Granted
- Kind: B2
- Application number: 16/100,285
- Filed: 2018-08-10
- Published: 2019-06-20
- Granted: 2020-12-22
- Earliest claimed: 2017-12-19
- Assignees: Samsung Electronics Co., Ltd.
- Applicants: Samsung Electronics Co., Ltd.
- Inventors: Kyoung-Seok Moon; Hyeon Cheol Park; Chan Kwak; Hyun Sik Kim; Daejin Yang; Youngjin Cho
- Web page: https://patentgrep.com/patent/US10872725B2

## CPC

- H01G 4/1227: {based on alkaline earth titanates}
- H01G 4/008: Selection of materials
- H01G 4/30: Stacked capacitors (H01G4/33 takes precedence)
- H01G 4/385: {Single unit multiple capacitors, e.g. dual capacitor in one coil}
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)

## Abstract

A ceramic dielectric includes a plurality of semi-conductive grains including a semiconductor oxide including barium (Ba), titanium (Ti), and a rare earth element. A ceramic dielectric also includes an insulative oxide located between adjacent semiconductor grains and an acceptor element including manganese (Mn), magnesium (Mg), aluminum (Al), iron (Fe), scandium (Sc), gallium (Ga), or a combination thereof, a method of manufacturing the ceramic dielectric, and a ceramic electronic component, and an electronic device including the ceramic dielectric.

## Claims

### Claim 1

A ceramic dielectric comprising:
a plurality of semiconductor grains, wherein one or more of the semiconductor grains comprises a semiconductor oxide, wherein the semiconductor oxide comprises barium, titanium, and at least one rare earth element; and
an insulative oxide between adjacent semiconductor grains and including an acceptor element, wherein the acceptor element comprises manganese, magnesium, aluminum, iron, scandium, gallium, or a combination thereof, wherein an amount of the acceptor element is about 0.5 mole to about 2 mole with respect to 100 mole of titanium.

### Claim 2 (depends on 1)

The ceramic dielectric of claim 1, wherein a distribution of the rare earth element is distributed throughout the entirety of the one or more semiconductor grains.

### Claim 3 (depends on 1)

The ceramic dielectric of claim 1, wherein one or more of the semiconductor grains further comprises a surface and a center, wherein a concentration of the rare earth element is uniform from the surface to the center of the semiconductor grain.

### Claim 4 (depends on 1)

The ceramic dielectric of claim 1, wherein the semiconductor oxide comprises a crystal structure, wherein the crystal structure comprises an oxygen vacancy.

### Claim 5 (depends on 1)

The ceramic dielectric of claim 1, wherein the semiconductor oxide comprises a perovskite structure, wherein the semiconductor oxide comprises BaTiO3, and wherein the rare earth element is a donor element that substitutes a portion of a barium site in the BaTiO3.

### Claim 6 (depends on 1)

The ceramic dielectric of claim 1, wherein one or more of the semiconductor grains comprises a semiconductor oxide represented by Chemical Formula 1:
(Ba1−xREx)TiO3-δ Chemical Formula 1
wherein, in Chemical Formula 1,
RE is at least one rare earth element,
0<x≤0.02, and
0<δ<3.

### Claim 7 (depends on 1)

The ceramic dielectric of claim 1, wherein the rare earth element comprises lanthanum, yttrium, bismuth, dysprosium, neodymium, samarium, holmium, or a combination thereof.

### Claim 8 (depends on 1)

The ceramic dielectric of claim 1, wherein an amount of the rare earth element is less than or equal to about 1 mole with respect to 100 mole of titanium.

### Claim 9 (depends on 1)

The ceramic dielectric of claim 1, wherein the insulative oxide is represented by Chemical Formula 2:
M2O3 Chemical Formula 2
wherein, in Chemical Formula 2,
M is manganese, magnesium, aluminum, iron, scandium, gallium, or a combination thereof.

### Claim 10 (depends on 1)

The ceramic dielectric of claim 1, wherein the insulative oxide forms a grain boundary located between adjacent semiconductor grains.

### Claim 11 (depends on 10)

The ceramic dielectric of claim 10, wherein the semiconductor grain includes the acceptor element of the grain boundary, and
the acceptor element is distributed within about 10% of a particle diameter of the semiconductor grain from a surface of the semiconductor grain.

### Claim 12 (depends on 11)

The ceramic dielectric of claim 11, wherein the grain boundary comprises an amount of the acceptor element that is greater than or equal to about 1.2 times an amount of the acceptor element in the plurality of semiconductor grains.

### Claim 13 (depends on 1)

The ceramic dielectric of claim 1, wherein the ceramic dielectric has a dielectric constant of greater than or equal to about 6,000 and/or a resistivity of greater than or equal to about 1×1010 ohm centimeters at room temperature.

### Claim 14

A ceramic dielectric comprising:
a grain comprising:
barium;
titanium; and
a donor element comprising lanthanum, yttrium, bismuth, dysprosium, neodymium, samarium, holmium, or a combination thereof; and
a grain boundary comprising an acceptor element, wherein the acceptor element comprises manganese, magnesium, aluminum, iron, scandium, gallium, or a combination thereof, wherein an amount of the acceptor element is about 0.5 mole to about 2 mole with respect to 100 mole of titanium,
wherein the barium, the titanium, and the donor element are non-locally distributed in the grain.

### Claim 15 (depends on 14)

The ceramic dielectric of claim 14, wherein the grain comprises a crystal structure, wherein the crystal structure comprises an oxygen vacancy.

### Claim 16 (depends on 14)

The ceramic dielectric of claim 14, wherein an amount of the donor element is less than or equal to about 1 mole with respect to 100 mole of titanium.

### Claim 17 (depends on 14)

The ceramic dielectric of claim 14, wherein the grain comprises the acceptor element diffused from the grain boundary and
the acceptor element is distributed within about 10% of a particle diameter of the grain from a surface of the grain.

### Claim 18 (depends on 14)

The ceramic dielectric of claim 14, wherein the grain is a semiconductor and/or the grain boundary is an insulator.

### Claim 19

A method of manufacturing a ceramic dielectric, the method comprising:
heating a barium precursor, a titanium precursor, and a rare earth element precursor to obtain a barium titanium oxide doped with a rare earth element;
mixing the barium titanium oxide doped with the rare earth element with an acceptor element precursor to obtain a mixture, wherein the acceptor element precursor comprises manganese, magnesium, aluminum, iron, scandium, gallium, or a combination thereof, wherein an amount of the acceptor element is about 0.5 mole to about 2 mole with respect to 100 mole of titanium; and
sintering the mixture to obtain a plurality of grains comprising the barium titanium oxide doped with the rare earth element and an insulative oxide located between adjacent grains,
wherein sintering the mixture comprises:
primary heat treatment under a reduction atmosphere, and
secondary heat treatment under an oxidizing atmosphere.

### Claim 20 (depends on 19)

The method of claim 19, wherein an amount of the rare earth element precursor is less than or equal to about 1 mole with respect to 100 mole of the titanium precursor.

### Claim 21 (depends on 19)

The method of claim 19, wherein the reduction atmosphere comprises a N2/H2 mixed gas and wherein a temperature of the reduction atmosphere is about 1100° C. to about 1400° C.

### Claim 22 (depends on 19)

The method of claim 19, wherein the oxidizing atmosphere comprises air and/or wet N2 and wherein a temperature of the oxidizing atmosphere is about 600° C. to about 800° C.

### Claim 23 (depends on 19)

The method of claim 19, further comprising compression-molding the mixture prior to sintering the mixture.

### Claim 24

A ceramic electronic component, comprising
a pair of electrodes facing each other; and
a ceramic dielectric layer located between the pair of electrodes,
wherein the ceramic dielectric layer comprises:
a plurality of semiconductor grains, wherein one or more of the semiconductor grains comprises a semiconductor oxide, wherein the semiconductor oxide comprises barium, titanium, and a rare earth element; and
an insulative oxide comprising an acceptor element, wherein the insulative oxide is located between adjacent semiconductor grains and wherein the acceptor element comprises manganese, magnesium, aluminum, iron, scandium, gallium, or a combination thereof, wherein an amount of the acceptor element is about 0.5 mole to about 2 mole with respect to 100 mole of titanium.

### Claim 25 (depends on 24)

The ceramic electronic component of claim 24, wherein
the ceramic electronic component comprises a multilayer ceramic capacitor, wherein the multilayer ceramic capacitor comprises a plurality of unit capacitors, and wherein the pair of electrodes and/or the ceramic dielectric layer are laminated.

### Claim 26 (depends on 24)

An electronic device comprising the ceramic electronic component of claim 24.