# US 7,745,869 B2 · Thin film capacitance element composition, high permittivity insulation film, thin film capacitance element, thin film multilayer capacitor and production method of thin film capacitance element

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- Number: US 7,745,869 B2
- Document ID: US7745869B2
- Status: Granted
- Kind: B2
- Application number: 10/542,956
- Filed: 2004-01-16
- Published: 2006-11-09
- Granted: 2010-06-29
- Earliest claimed: 2003-01-21
- Assignees: TDK Corporation
- Inventors: Yukio Sakashita
- Web page: https://patentgrep.com/patent/US7745869B2

## CPC

- H01G 4/1218: {based on titanium oxides or titanates (H01G4/1245 takes precedence)}
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- C01G 29/00: Compounds of bismuth
- C04B 35/475: based on bismuth titanates
- C04B 35/6264: {Mixing media, e.g. organic solvents}
- H01B 3/12: ceramics
- H01G 4/30: Stacked capacitors (H01G4/33 takes precedence)
- C01P 2002/20: Two-dimensional structures
- C01P 2002/52: containing elements as dopants
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- C01P 2006/40: Electric properties
- 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 2235/3224: Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B 2235/441: Alkoxides, e.g. methoxide, tert-butoxide
- C04B 2235/6585: at an oxygen percentage above that of air
- C04B 2235/787: Oriented grains
- C04B 2235/79: Non-stoichiometric products, e.g. perovskites (ABO3) with an A/B-ratio other than 1
- 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)
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- 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
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

A thin film capacitance element composition, wherein a bismuth layer compound having a c-axis oriented vertically with respect to a substrate surface is expressed by a composition formula of (Bi2O2)2+(Am−1BmO3m+1)2− or Bi2Am−1BmO3m+3, wherein “m” is an even number, “A” is at least one element selected from Na, K, Pb, Ba, Sr, Ca and Bi, and “B” is at least one element selected from Fe, Co, Cr, Ga, Ti, Nb, Ta, Sb, V, Mo and W; and Bi in the bismuth layer compound is excessively included with respect to the composition formula of (Bi2O2)2+(Am−1BmO3m+1)2− or Bi2Am−1BmO3m+3, and the excessive content of Bi is in a range of 0<Bi<0.5×m mol in of Bi.

## Claims

### Claim 1

A thin film capacitance element, comprising a lower portion electrode, a dielectric thin film including a bismuth layer compound having a c-axis oriented vertically with respect to a substrate surface, and an upper portion electrode are successively formed on the substrate, wherein:
the bismuth layer compound is composed of a thin film capacitance element composition;
the bismuth layer compound is expressed by a composition formula of (Bi2O2)2+(Am−1BmO3m+1)2− or Bi2Am−1BmO3m+3, wherein:
“m” is an even number,
“A” is at least one element selected from Na, K, Pb, Ba, Sr, Ca and Bi, and
“B” is at least one element selected from Fe, Co, Cr, Ga, Ti, Nb, Ta, Sb, V, Mo and W;
Bi in said bismuth layer compound is excessively included with respect to said composition formula of (Bi2O2)2+(Am−1BmO3m+1)2− or Bi2Am−1BmO3m+3, and the excessive content of Bi is in a range of 0<Bi<0.5×m mol in terms of Bi;
a c-axis orientation degree of the bismuth layer compound is 80% or higher; and
the lower portion electrode is oriented in a [100] direction.

### Claim 2 (depends on 1)

The thin film capacitance element set forth in claim 1, wherein the excessive content of Bi in the dielectric thin film is in a range of 0.4≦Bi<0.5×m mol in terms of Bi.

### Claim 3 (depends on 1)

The thin film capacitance element as set forth in claim 1, the thin film capacitance element composition further comprising at least one rare earth element selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.

### Claim 4 (depends on 1)

The thin film capacitance element as set forth in claim 1, wherein leakage current density at electric field intensity of 50 kV/cm is 1×10−7 A/cm2 or lower.

### Claim 5 (depends on 1)

The thin film capacitance element set forth in claim 1, wherein an average change rate of a capacitance against a temperature in a range of −55 to +150° C. is ±500 ppm/° C. with the reference temperature of 25° C.

### Claim 6 (depends on 1)

The thin film capacitance element as set forth in claim 1, wherein a thickness of said dielectric thin film is 1 to 1000 nm.

### Claim 7 (depends on 1)

The thin film capacitance element as set forth in claim 1, wherein the lower portion electrode comprises a conductive oxide or precious metal.

### Claim 8 (depends on 1)

The thin film capacitance element as set forth in claim 1, wherein the lower portion electrode comprises CaRuO3, SrRuO3, Pt, or Ru.

### Claim 9

A thin film capacitance element, comprising a lower portion electrode, a dielectric thin film including a bismuth layer compound having a c-axis oriented vertically with respect to a substrate surface, and an upper portion electrode are successively formed on the substrate, wherein:
the bismuth layer compound is composed of a thin film capacitance element composition;
the bismuth layer compound is expressed by a composition formula of SrBi4Ti4O15;
Bi in the bismuth layer compound is excessively included with respect to said composition formula of SrBi4Ti4O15, and the excessive content of Bi is in a range of 0<Bi<2.0 mol in terms of Bi;
a c-axis orientation degree of the bismuth layer compound is 80% or higher; and
the lower portion electrode is oriented in a [100] direction.

### Claim 10

A thin film capacitance element, comprising a lower portion electrode, a dielectric thin film including a bismuth layer compound having a c-axis oriented vertically with respect to a substrate surface, and an upper portion electrode are successively formed on the substrate, wherein:
the bismuth layer compound is composed of a thin film capacitance element composition;
the bismuth layer compound is expressed by a composition formula of SrBi4Ti4O15;
Bi in the bismuth layer compound is excessively included with respect to said composition formula of SrBi4Ti4O15, and when the excessive content of Bi is expressed by a mole ratio (Bi/Ti) against Ti, Bi/Ti is in a range of 1<Bi/Ti<1.5;
a c-axis orientation degree of the bismuth layer compound is 80% or higher; and
the lower portion electrode is oriented in a [100] direction.

### Claim 11

A thin film capacitance element, comprising a lower portion electrode, a dielectric thin film including a bismuth layer compound having a c-axis oriented vertically with respect to a substrate surface, and an upper portion electrode are successively formed on the substrate, wherein:
the bismuth layer compound is composed of a thin film capacitance element composition;
the bismuth layer compound is expressed by a composition formula of SrxCayBazBi4Ti4O16, x+y+z=1, 0≦x≦1, 0≦y≦, and 0≦z≦1; and
Bi in the bismuth layer compound is excessively included with respect to said composition formula of SrxCayBazBi4Ti4O15, and when the excessive content of Bi is expressed by a mole ratio (Bi/Ti) against Ti, Bi/Ti is in a range of 1<Bi/Ti<1.5;
a c-axis orientation degree of the bismuth layer compound is 80% or higher; and
the lower portion electrode is oriented in a [100] direction.

### Claim 12

A thin film multilayer capacitor, comprising a plurality of dielectric thin films comprising a bismuth layer compound having a c-axis oriented vertically with respect to a substrate surface and internal electrode thin films alternately stacked on a substrate, wherein:
the bismuth layer compound is composed of a thin film capacitance element composition;
the bismuth layer compound is expressed by a composition formula of (Bi2O2)2+(Am−1BmO3m+1)2− or Bi2Am−1BmO3m+3, wherein:
“m” is an even number,
“A” is at least one element selected from Na, K, Pb, Ba, Sr, Ca, and Bi, and
“B” is at least one element selected from Fe, Co, Cr, Ga, Ti, Nb, Ta, Sb, V, Mo and W;
Bi in said bismuth layer compound is excessively included with respect to said composition formula of (Bi2O2)2+(Am−1BmO3m+1)2− or Bi2Am−1BmO3m+3, and the excessive content of Bi is in a range of 0<Bi<0.5×m mol in terms of Bi;
a c-axis orientation degree of the bismuth layer compound is 80% or higher; and
the internal electrode thin films are oriented in a [100] direction.

### Claim 13 (depends on 12)

The thin film multilayer capacitor as set forth in claim 12, wherein a thickness of said dielectric thin film is 1 to 1000 nm.