# US 12,015,073 B2 · Thin film structure including dielectric material layer and electronic device including the same

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- Number: US 12,015,073 B2
- Document ID: US12015073B2
- Status: Granted
- Kind: B2
- Application number: 17/984,877
- Filed: 2022-11-10
- Published: 2023-03-09
- Granted: 2024-06-18
- Earliest claimed: 2019-08-08
- Assignees: Samsung Electronics Co., Ltd.
- Applicants: Samsung Electronics Co., Ltd.
- Inventors: Woojin Lee; Kiyoung Lee; Yongsung Kim; Eunsun Kim
- Web page: https://patentgrep.com/patent/US12015073B2

## CPC

- H10D 64/689: {having ferroelectric layers}
- C01G 23/006: {Alkaline earth titanates}
- C01G 35/006: {Compounds containing tantalum, with or without oxygen or hydrogen, and containing two or more other elements}
- H10B 51/00: Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory transistors
- H10B 53/00: Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory capacitors
- H10D 1/682: {having dielectrics comprising perovskite structures}
- C01P 2002/34: perovskite-type (ABO3)
- C01P 2002/52: containing elements as dopants
- C01P 2002/77: by unit-cell parameters, atom positions or structure diagrams
- C01P 2006/40: Electric properties
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- 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)
- H10B: ELECTRONIC MEMORY DEVICES
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

A thin film structure including a dielectric material layer and an electronic device to which the thin film structure is applied are provided. The dielectric material layer includes a compound expressed by ABO3, wherein at least one of A and B in ABO3 is substituted and doped with another atom having a larger atom radius, and ABO3 becomes A1-xA′xB1-yB′yO3 (where x>=0, y>=0, at least one of x and y≠0, a dopant A′ has an atom radius greater than A and/or a dopant B′ has an atom radius greater than B) through substitution and doping. A dielectric material property of the dielectric material layer varies according to a type of a substituted and doped dopant and a substitution doping concentration.

## Claims

### Claim 1

A memory device comprising:
a dielectric material layer; and
first and second metal layers on both sides of the dielectric material layer,
wherein the dielectric material layer comprising a compound expressed by ABO3, wherein at least one of A and B in ABO3 is substituted and doped with another atom having a larger atom radius, and ABO3 becomes A1-xA′xB1-yB′yO3 through substitution and doping, where x>0, y>=0, and a dopant A′ has an atom radius greater than A and/or a dopant B′ has an atom radius greater than B,
wherein a dielectric material property of the dielectric material layer varies according to a type of a substituted and doped dopant and a substitution doping concentration, and
wherein A is Sr, B is Ti,
A′ is any one selected from Cs, Rb, and K, and
B′ is any one selected from Zr, Hf, Sn, Nb, and Ta.

### Claim 2 (depends on 1)

The memory device of claim 1, wherein atoms of A and A′, B and B′, or A+B and A′+B′ have same valence electron number.

### Claim 3 (depends on 1)

The memory device of claim 1, wherein a tensile strain is induced through substitution and doping such that the dielectric material layer converts a paraelectric material to a ferroelectric material or improves a dielectric constant.

### Claim 4 (depends on 1)

The memory device of claim 1, wherein the compound expressed by ABO3 is SrTiO3, and
Sr is substituted and doped with any one of Cs, Rb, and K, and Ti is substituted and doped with any one of Nb and Ta, or
Sr is substituted and doped with La and Ti is substituted and doped with any one of In, Sc, and Y.

### Claim 5 (depends on 4)

The memory device of claim 4, wherein Sr and Ti are substituted and doped with Cs and Nb, respectively, at 12.9 at. % or more,
Sr and Ti are substituted and doped with Cs and Ta, respectively, at 11.5 at. % or more,
Sr and Ti are substituted and doped with Rb and Nb, respectively, at 20.6 at. % or more,
Sr and Ti are substituted and doped with Rb and Ta, respectively, at 19.8 at. % or more,
Sr and Ti are substituted and doped with K and Nb, respectively, at 30.5 at. % or more,
Sr and Ti are substituted and doped with K and Ta, respectively, at 28.8 at. % or more,
Sr and Ti are substituted and doped with La and In, respectively, at 11.4 at. % or more,
Sr and Ti are substituted and doped with La and Sc, respectively, at 18.9 at. % or more, or
Sr and Ti are substituted and doped with La and Y, respectively, at 6.3 at. % or more.

### Claim 6 (depends on 1)

The memory device of claim 1,
wherein substitution and doping of any one of A and B or each of A and B of the dielectric material layer is performed in a range of 50% or less.

### Claim 7 (depends on 1)

The memory device of claim 1, wherein the first metal layer, the dielectric material layer, and the second metal layer constitute a capacitor in included in a unit cell of a DRAM device.

### Claim 8

A memory device comprising:
a dielectric material layer; and
first and second metal layers on both sides of the dielectric material layer,
wherein the dielectric material layer comprising a compound expressed by ABO3, wherein at least one of A and B in ABO3 is substituted and doped with another atom having a larger atom radius, and ABO3 becomes A1-xA′xB1-yB′yO3 through substitution and doping, where x>=0, y>0, and a dopant A′ has an atom radius greater than A and/or a dopant B′ has an atom radius greater than B,
wherein a dielectric material property of the dielectric material layer varies according to a type of a substituted and doped dopant and a substitution doping concentration, and
wherein A is Sr, B is Ti,
A′ is any one selected from Ba, Cs, Rb, and K, and
B′ is any one selected from Zr and Hf,
wherein the compound expressed by ABO3 is SrTiO3, and Ti is substituted and doped with any one of Zr and Hf.

### Claim 9 (depends on 8)

The memory device of claim 8, wherein Ti is substituted and doped with Zr at 11.4 at. % or more, Ti is substituted and doped with Hf at 15.1 at. % or more.

### Claim 10 (depends on 8)

The memory device of claim 8,
wherein Sr is substituted and doped with Ba at 32.3 at. % or more.

### Claim 11 (depends on 8)

The memory device of claim 8, wherein Sr is substituted and doped with Ba.

### Claim 12 (depends on 8)

The memory device of claim 8, wherein the first metal layer, the dielectric material layer, and the second metal layer constitute a capacitor in included in a unit cell of a DRAM device.

### Claim 13

A memory device comprising:
a dielectric material layer; and
first and second metal layers on both sides of the dielectric material layer,
wherein the dielectric material layer comprising a compound expressed by ABO3, wherein at least one of A and B in ABO3 is substituted and doped with another atom having a larger atom radius, and ABO3 becomes A1-xA′xB1-yB′yO3 through substitution and doping, where x>=0, y>=0, at least one of x and y≠0 and a dopant A′ has an atom radius greater than A and/or a dopant B′ has an atom radius greater than B,
wherein a dielectric material property of the dielectric material layer varies according to a type of a substituted and doped dopant and a substitution doping concentration, and
wherein A is K and B is Ta,
A′ is any one selected from Cs, Rb, Ba, and La, and
B′ is any one selected from In, Sc, Y, Hf, Sn, and Zr.

### Claim 14 (depends on 13)

The memory device of claim 13, wherein the compound expressed by ABO3 is KTaO3,K is substituted and doped with Cs at 24.7 at. % or more and 50 at. % or less, or K is substituted and doped with Rb at 71.3 at. % or more.

### Claim 15 (depends on 13)

The memory device of claim 13,
wherein the compound expressed by ABO3 is KTaO3, K and Ta are substituted and doped,
K and Ta are substituted and doped with Ba and In, respectively, at 7.8 at. % or more,
K and Ta are substituted and doped with Ba and Sc, respectively, at 9.8 at. % or more, or K and Ta are substituted and doped with Ba and Y, respectively, at 5.0 at. % or more.

### Claim 16 (depends on 15)

The memory device of claim 15, wherein substitution and doping of A of the dielectric material layer is performed in a range of 50% or less, substitution and doping of B is performed in a range of 25% or less, and
substitution and doping of A and B is performed at a ratio of 2:1.

### Claim 17 (depends on 13)

The memory device of claim 13,
wherein the compound expressed by ABO3 is KTaO3,
K and Ta are substituted and doped with Ba and Hf, respectively, at 14.4 at. % or more,
K and Ta are substituted and doped with Ba and Sn, respectively, at 17.9 at. % or more,
K and Ta are substituted and doped with Ba and Zr, respectively, at 10.7 at. % or more,
K and Ta are substituted and doped with La and In, respectively, at 13.9 at. % or more,
K and Ta are substituted and doped with La and Sc, respectively, at 22.3 at. % or more, or
K and Ta are substituted and doped with La and Y, respectively, at 7.4 at. % or more.

### Claim 18 (depends on 13)

The memory device of claim 13, wherein the first metal layer, the dielectric material layer, and the second metal layer constitute a capacitor included in a unit cell of a DRAM device.