Thin film structure including method of manufacturing

Patent metadata

Field	Value
Publication number	US-12308365-B2
Application number	US-202217844896-A
Country	US
Kind code	B2
Filing date	Jun 21, 2022
Priority date	Jun 21, 2021
Publication date	May 20, 2025
Grant date	May 20, 2025

Abstract

Provided are a thin film structure, a capacitor including the thin film structure, a semiconductor device including the thin film structure, and a method of manufacturing the thin film structure, in which the thin film structure may include: a first electrode thin film disposed on a substrate and including a first perovskite-based oxide; and a protective film disposed on the first electrode thin film and including a second perovskite-based oxide that is oxygen-deficient and includes a doping element. The thin film structure may prevent the deterioration of conductivity and a crystalline structure of a perovskite-based oxide electrode, which is a lower electrode, even in a high-temperature oxidizing atmosphere for subsequent dielectric film deposition.

First claim

What is claimed is:

1. A thin film structure comprising:
a first electrode thin film on a substrate and including a first perovskite-based oxide; and
a protective film on the first electrode thin film and including a second perovskite-based oxide that is oxygen-deficient and comprises a doping element.

2. The thin film structure of claim 1 , wherein the second perovskite-based oxide is represented by Formula 1:
X 1-a Z a YO 3-δ   Formula 1

wherein, in Formula 1,
X is a divalent element,
Y is a quadvalent element,
Z is a doping element that, through doping, causes a biaxial strain ratio of the second perovskite-based oxide to be less than or equal to −1% and greater than or equal to −3%, and
0<a<1 and 0<δ<0.5.

3. The thin film structure of claim 2 , wherein X in Formula 1 is at least one element selected from Sr, Ca, and Ba.

4. The thin film structure of claim 2 , wherein Y in Formula 1 is at least one element selected from Ti, Zr, and Hf.

5. The thin film structure of claim 2 , wherein Z in Formula 1 is at least one of Ce, La, Pr, Sn, Ge, N, V.

6. The thin film structure of claim 2 , wherein a and δ in Formula 1 are respectively in a range of 0.01≥a≥0.5 and 0.05≥δ≥0.3.

7. The thin film structure of claim 1 , wherein the second perovskite-based oxide is represented by Formula 2:
Sr 1-a Z′ a TiO 3-δ   Formula 2

wherein, in Formula 2,
Z′ is at least one of Ce, La, Pr, Sn, Ge, N, V, and
0.01≥a≥0.5 and 0.05≥δ≥0.3.

8. The thin film structure of claim 1 , wherein the second perovskite-based oxide includes at least one of Sr 1-a Ce a TiO 3-δ , Sr 1-a La a TiO 3-δ , Sr 1-a Pr a TiO 3-δ , Sr 1-a Sn a TiO 3-δ , Sr 1-a Ge a TiO 3-δ , Sr 1-a N a TiO 3-δ , Sr 1-a V a TiO 3-δ , Sr 1-a Ce a ZrO 3-δ , Sr 1-a La a ZrO 3-δ , Sr 1-a Pr a ZrO 3-δ , Sr 1-a Sn a ZrO 3-δ , Sr 1-a Ge a ZrO 3-δ , Sr 1-a N a ZrO 3-δ , Sr 1-a V a ZrO 3-δ , Sr 1-a Ce a HfO 3-δ , Sr 1-a La a HfO 3-δ , Sr 1-a Pr a HfO 3-δ , Sr 1-a Sn a HfO 3-δ , Sr 1-a Ge a HfO 3-δ , Sr 1-a N a HfO 3-δ , Sr 1-a V a HfO 3-δ , Ca 1-a Ce a TiO 3-δ , Ca 1-a La a TiO 3-δ , Ca 1-a Pr a TiO 3-δ , Ca 1-a Sn a TiO 3-δ , Ca 1-a Ge a TiO 3-δ , Ca 1-a N a TiO 3-δ , Ca 1-a V a TiO 3-δ , Ca 1-a Ce a ZrO 3-δ , Ca 1-a La a ZrO 3-δ , Ca 1-a Pr a ZrO 3-δ , Ca 1-a Sn a ZrO 3-δ , Ca 1-a Ge a ZrO 3-δ , Ca 1-a N a ZrO 3-δ , Ca 1-a V a ZrO 3-δ , Ca 1-a Ce a HfO 3-δ , Ca 1-a La a HfO 3-δ , Ca 1-a Pr a HfO 3-δ , Ca 1-a Sn a HfO 3-δ , Ca 1-a Ge a HfO 3-δ , Ca 1-a N a HfO 3-δ , Ca 1-a V a HfO 3-δ , Ba 1-a Ce a TiO 3-δ , Ba 1-a La a TiO 3-δ , Ba 1-a Pr a TiO 3-δ , Ba 1-a Sn a TiO 3-δ , Ba 1-a Ge a TiO 3-δ , Ba 1-a N a TiO 3-δ , Ba 1-a V a TiO 3-δ , Ba 1-a Ce a ZrO 3-δ , Ba 1-a La a ZrO 3-δ , Ba 1-a Pr a ZrO 3-δ , Ba 1-a Sn a ZrO 3-δ , Ba 1-a Ge a ZrO 3-δ , Ba 1-a N a ZrO 3-δ , Ba 1-a V a ZrO 3-δ , Ba 1-a Ce a HfO 3-δ , Ba 1-a La a HfO 3-δ , Ba 1-a Pr a HfO 3-δ , Ba 1-a Sn a HfO 3-δ , Ba 1-a Ge a HfO 3-δ , Ba 1-a N a HfO 3-δ , or Ba 1-a V a HfO 3-δ ,
wherein, in the above formulae, a is greater than or equal to 0.01 to and less than or equal to 0.5, and δ is greater than or equal to 0.05 and less than or equal to 0.3.

9. The thin film structure of claim 1 , wherein a thickness of the protective film is 4.5 nanometers (nm) or greater and 1,000 nm or less.

10. The thin film structure of claim 1 , wherein the first perovskite-based oxide is at least one selected from compounds represented by Formulae 3 and 4:
ABO 3   Formula 3

wherein, in Formula 3,
A is at least one element selected from Sr, Ca, and Ba, and
B is at least one element selected from Ru, Nb, V, Ti, Fe, and Co,
La 1-a A a MO 3   Formula 4

in Formula 4, A is at least one element selected from Sr, Ca, and Ba, and
M is at least one element selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Al, and Ru.

11. The thin film structure of claim 1 , wherein the first perovskite-based oxide comprises at least one of SrRuO 3 , SrNbO 3 , SrVO 3 , CaRuO 3 , CaNbO 3 , CaVO 3 .

12. The thin film structure of claim 1 , wherein the substrate comprises a third perovskite-based oxide.

13. The thin film structure of claim 1 , wherein the substrate is a single crystalline substrate comprising at least one of SrTiO 3 , La-doped SrTiO 3 , Nb-doped SrTiO 3 , LaAlO 3 , KTaO 3 , LaSrAlO 4 , (LaAlO 3 ) 0.3 (Sr 2 TaAlO 6 ) 0.7 , YAlO 3 , DyScO 3 , TbScO 3 , GdScO 3 , EuScO 3 , SmScO 3 , NdScO 3 , PrScO 3 , CeScO 3 , LaScO 3 .

14. The thin film structure of claim 1 , wherein the first electrode thin film is a film having a property wherein a perovskite crystalline structure of the first electrode thin film is maintained after exposure to a high-temperature oxidizing environment of 300° C. or greater.

15. The thin film structure of claim 1 , further comprising:
a dielectric material thin film on the protective film and comprising a fourth perovskite-based oxide.

16. The thin film structure of claim 15 , further comprising:
a second electrode thin film comprising a fifth perovskite-based oxide, the second electrode thin film on the dielectric material thin film.

Assignees

• Samsung Electronics Co Ltd

Inventors

• Kim Hyungjun
• Lee Changsoo
• Cho Yong-Hee
• Kim Yongsung
• Lee Jooho

Classifications

• H10B12/373

  the capacitor extending under or around the transistor · CPC title

• H10B12/377

  having a storage electrode extension located over the transistor · CPC title

• H10D1/684 Primary

  the dielectrics comprising multiple layers, e.g. comprising buffer layers, seed layers or gradient layers · CPC title

• H01L28/56 Primary

  Electricity · mapped topic