# US 2017/0287635 A1 · Dielectric ceramic composition and multilayer ceramic capacitor

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- Number: US 2017/0287635 A1
- Document ID: US20170287635A1
- Status: Published application
- Kind: A1
- Application number: 15/466,224
- Filed: 2017-03-22
- Published: 2017-10-05
- Earliest claimed: 2016-03-30
- Assignees: TDK Corporation
- Applicants: TDK Corporation
- Inventors: Dan SAKURAI; Nobuto MORIGASAKI; Tatsuya ISHII; Takuma ARIIZUMI; Shinsuke HASHIMOTO; Yasuhiro ITO
- Web page: https://patentgrep.com/patent/US20170287635A1

## CPC

- H01G 4/1245: {containing also titanates}
- C01G 25/006: {Compounds containing zirconium, with or without oxygen or hydrogen, and containing two or more other elements}
- C04B 35/4682: {based on BaTiO3 perovskite phase}
- C04B 35/49: containing also titanium oxides or titanates
- C04B 35/6261: {Milling}
- C04B 35/62675: {characterised by the treatment temperature}
- C04B 35/6303: {Inorganic additives}
- C04B 35/638: Removal thereof
- C04B 35/64: Burning or sintering processes (C04B33/32 takes precedence {; powder metallurgy B22F})
- H01G 4/012: Form of non-self-supporting electrodes
- H01G 4/1227: {based on alkaline earth titanates}
- H01G 4/248: the terminals embracing or surrounding the capacitive element, e.g. caps (H01G4/252 takes precedence)
- C04B 2235/3203: Lithium oxide or oxide-forming salts thereof
- C04B 2235/3206: Magnesium oxides or oxide-forming salts thereof
- C04B 2235/3208: Calcium oxide or oxide-forming salts thereof, e.g. lime
- C04B 2235/3213: Strontium oxides or oxide-forming salts thereof
- C04B 2235/3215: Barium oxides or oxide-forming salts thereof
- C04B 2235/3217: Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B 2235/3224: Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B 2235/3225: Yttrium oxide or oxide-forming salts thereof
- C04B 2235/3227: Lanthanum oxide or oxide-forming salts thereof
- C04B 2235/3229: Cerium oxides or oxide-forming salts thereof
- C04B 2235/3236: Alkaline earth titanates
- C04B 2235/3241: Chromium oxides, chromates, or oxide-forming salts thereof
- C04B 2235/3249: containing also titanium oxide or titanates, e.g. lead zirconate titanate (PZT)
- C04B 2235/3262: Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
- C04B 2235/3272: Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
- C04B 2235/3275: Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
- C04B 2235/3287: Germanium oxides, germanates or oxide forming salts thereof, e.g. copper germanate
- C04B 2235/3409: Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
- C04B 2235/3418: Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
- C04B 2235/652: Reduction treatment (C04B2235/664 takes precedence)
- C04B 2235/6562: Heating rate
- C04B 2235/6565: Cooling rate
- C04B 2235/6567: Treatment time
- C04B 2235/6584: at an oxygen percentage below that of air
- C04B 2235/662: Annealing after sintering
- C04B 2235/768: Perovskite structure ABO3
- C04B 2235/81: Materials characterised by the absence of phases other than the main phase, i.e. single phase materials
- C04B 2235/96: Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- H01G 4/30: Stacked capacitors (H01G4/33 takes precedence)
- 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)
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE

## Abstract

A dielectric ceramic composition having good characteristic even under high electric field intensity, and particularly good IR characteristic and high temperature accelerated lifetime. The present invention is a dielectric ceramic composition comprising, a main component comprising a perovskite type compound shown by a compositional formula (Ba1-x-ySrxCay)m(Ti1-zZrz)O3, a first sub component comprising oxides of a rare earth element, a second sub component as a sintering agent, wherein said dielectric ceramic composition is a complete solid solution particle wherein the rare earth element is solid dissolved to entire dielectric particle, or a core-shell particle having high ratio of the diffusion phase, and comprises the dielectric particle having 5 to 20 atom % of the average concentration of the rare earth element in the diffusion phase, and having uniform concentration distribution of the rare earth element in the diffusion phase.

## Claims

### Claim 1

A dielectric ceramic composition comprising,
a main component comprising a perovskite type compound shown by a compositional formula (Ba1-x-ySrxCay)m(Ti1-zZrZ)O3 and “z” all show a mol ratio, and each satisfies 0.94<m<1.1, 0<x<1.0, 0<y<1.0, 0<(x+y)<1.0, 0.06<z<0.2),
a first sub component comprising oxides of a rare earth element R (note that, R is at least one selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu),
a second sub component as a sintering agent, wherein
said dielectric ceramic composition comprises a dielectric particle and a particle boundary,
said dielectric particle comprises a complete solid solution particle wherein the rare earth element R is solid dissolved to entire dielectric particle,
when a concentration of Ti atom in said complete solid solution particle is 100 atom %, then an average concentration Ra of the rare earth element R in said complete solid solution particle is 5 to 20 atom %,
when the rare earth element concentration (atom %) is measured at a part excluding an area 20 nm or less from the particle boundary of said complete solid solution particle, then a standard deviation and an average value of a measured values satisfies (standard deviation/average value)<0.25.

### Claim 2 (depends on 1)

The dielectric ceramic composition as set forth in claim 1, wherein said (standard deviation/average value) satisfies (standard deviation/average value)<0.10.

### Claim 3

A dielectric ceramic composition comprising,
a main component comprising a perovskite type compound shown by a compositional formula (Ba1-x-ySrxCay)m(Ti1-zZrz)O3 (note that, said “m”, “x”, “y” and “z” all show a mol ratio, and each satisfies 0.94<m<1.1, 0<x<1.0, 0<y<1.0, 0<(x+y)<1.0, 0.06<z<0.2),
a first sub component comprising oxides of a rare earth element R (note that, R is at least one selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu),
a second sub component as a sintering agent, wherein
said dielectric ceramic composition comprises a dielectric particle and a particle boundary,
said dielectric particles comprises a main component phase made of said main component, and a diffusion phase wherein said first sub component is diffused in said main component,
a ratio of area occupied by said diffusion phase is 95% or more and less than 100% in average with respect to a total area of said main component phase and said diffusion phase,
when a concentration of Ti atom in said diffusion phase is 100 atom %, then an average concentration Ra of the rare earth element R in the diffusion phase is 5 to 20 atom %,
when the rare earth element concentration (atom %) is measured at a part excluding an area 20 nm or less from the particle boundary of said complete solid solution particle and at the diffusion phase excluding the area 20 nm or less from the boundary between the main component phase and the diffusion phase, then a standard deviation and an average value of a measured values satisfies (standard deviation/average value)<0.25.

### Claim 4 (depends on 3)

The dielectric ceramic composition as set forth in claim 3, wherein said (standard deviation/average value) satisfies (standard deviation/average value)<0.10.

### Claim 5 (depends on 3)

The dielectric ceramic composition as set forth in claim 3, the ratio of area occupied by said diffusion phase is 98% or more and less than 100% in average with respect to the total area of said main component phase and said diffusion phase.

### Claim 6 (depends on 4)

The dielectric ceramic composition as set forth in claim 4, the ratio of area occupied by said diffusion phase is 98% or more and less than 100% in average with respect to the total area of said main component phase and said diffusion phase.

### Claim 7 (depends on 1)

An electronic component including the dielectric ceramic composition as set forth in claim 1.

### Claim 8 (depends on 1)

A multilayer ceramic capacitor comprising a dielectric layer including the dielectric ceramic composition as set forth in claim 1, and an internal electrode layer.