Dielectric monolayer thin film, capacitor and semiconductor device each including the same, and method of forming the dielectric monolayer thin film

Patent metadata

Field	Value
Publication number	US-11763989-B2
Application number	US-202017038904-A
Country	US
Kind code	B2
Filing date	Sep 30, 2020
Priority date	Oct 10, 2019
Publication date	Sep 19, 2023
Grant date	Sep 19, 2023

Abstract

Provided are a dielectric monolayer thin film, a capacitor and a semiconductor device each including the dielectric monolayer thin film, and a method of forming the dielectric monolayer thin film, the dielectric monolayer thin film including an oxide which is represented by Formula 1 and has a perovskite-type crystal structure, wherein the oxide has a surface chemically bonded with hydrogen.A2Bn−3CnO3n+1  <Formula 1>wherein, in Formula 1, A is a divalent element,B is a monovalent element,C is a pentavalent element, andn is a number from 3 to 8.

First claim

What is claimed is:

1. A dielectric monolayer thin film comprising:
an oxide represented by Formula 1, the oxide having a perovskite-type crystal structure and having a surface chemically bonded with hydrogen,
A 2 B n−3 C n O 3n+1   <Formula 1>

wherein, in Formula 1, A is a divalent element,
B is a monovalent element,
C is a pentavalent element, and
n is a number from 3 to 8.

2. The dielectric monolayer thin film of claim 1 , wherein, in Formula 1, A is at least one of Ca, Sr, and Ba.

3. The dielectric monolayer thin film of claim 1 , wherein, in Formula 1, B is at least one of Na, K, Rb, and Cs.

4. The dielectric monolayer thin film of claim 1 , wherein, in Formula 1, C is at least one of V, Nb, and Ta.

5. The dielectric monolayer thin film of claim 1 , wherein the oxide is a compound represented by Formula 2:
Sr 2 Na n−3 Nb n O 3n+1   <Formula 2>

wherein, in Formula 2, n is 3, 4, 5, or 6.

6. The dielectric monolayer thin film of claim 1 , wherein the dielectric monolayer thin film has a thickness of about 5 nm or smaller.

7. The dielectric monolayer thin film of claim 1 , wherein the oxide represented by Formula 1 is at least one of Sr 2 Nb 3 O 10 , Sr 2 NaNb 4 O 13 , Sr 2 Na 2 Nb 5 O 16 , Sr 2 NaTa 4 O 13 , Sr 2 Na 2 Ta 5 O 16 , Sr 2 KNb 4 O 13 , Sr 2 K 2 Nb 5 O 16 , Sr 2 RbNb 4 O 13 , Sr 2 Rb 2 Nb 5 O 16 , Ca 2 Nb 3 O 10 , Ca 2 NaNb 4 O 13 , Ca 2 Na 2 Nb 5 O 16 , Ca 2 KNb 4 O 13 , Ca 2 K 2 Nb 5 O 16 , Ca 2 RbNb 4 O 13 , Ca 2 Rb 2 Nb 5 O 16 , Ca 2 Ta 3 O 10 , Ca 2 NaTa 4 O 13 , Ca 2 Na 2 Ta 5 O 16 , Ca 2 KTa 4 O 13 , Ca 2 K 2 Ta 5 O 16 , Ca 2 RbTa 4 O 13 , Ca 2 Rb 2 Ta 5 O 16 , Ba 2 Nb 3 O 10 , Ba 2 NaNb 4 O 13 , Ba 2 Na 2 Nb 5 O 16 , Ba 2 KNb 4 O 13 , Ba 2 K 2 Nb 5 O 16 , Ba 2 RbNb 4 O 13 , Ba 2 Rb 2 Nb 5 O 16 , Ba 2 Ta 3 O 10 , Ba 2 NaTa 4 O 13 , Ba 2 Na 2 Ta 5 O 16 , Ba 2 KTa 4 O 13 , Ba 2 K 2 Ta 5 O 16 , Ba 2 RbTa 4 O 13 , and Ba 2 Rb 2 Ta 5 O 16 .

8. The dielectric monolayer thin film of claim 1 , wherein the dielectric monolayer thin film has a dielectric constant of about 400 or greater at 100 KHz.

9. The dielectric monolayer thin film of claim 1 , wherein the oxide having the surface chemically bonded with hydrogen has a band gap of about 3 eV or greater.

10. The dielectric monolayer thin film of claim 1 , wherein the oxide having the surface chemically bonded with hydrogen does not exhibit a C—H absorption peak in a wave number region of about 2800 cm −1 to 3200 cm −1 , and exhibits an O—H absorption peak in a wave number region of about 3250 cm −1 to about 3800 cm −1 , as measured by infrared spectroscopy.

11. The dielectric monolayer thin film of claim 1 , wherein the oxide having the surface chemically bonded with hydrogen has a carbon content of 1% or smaller, as measured by liquid chromatography.

12. A capacitor comprising:
a first electrode;
a second electrode; and
the dielectric monolayer thin film according to claim 1 between the first electrode and the second electrode.

13. A semiconductor device comprising the dielectric monolayer thin film according to claim 1 .

14. A method of forming a dielectric monolayer thin film having a surface chemically bounded with hydrogen, the method comprising:
forming a dielectric monolayer thin film comprising an oxide which is represented by Formula 1 and a perovskite-type crystal structure; and
treating the dielectric monolayer thin film with UV and reactive gas, thereby forming the dielectric monolayer thin film including the oxide which is represented by Formula 1, has the perovskite-type crystal structure, and has a surface chemically bonded with hydrogen:
A 2 B n−3 C n O 3n+1   <Formula 1>

wherein, in Formula 1, A is a divalent element, B is a monovalent element, C is a pentavalent element, and n is a number from 3 to 8.

15. The method of claim 14 , wherein the reactive gas comprises at least one of ozone (O 3 ), oxygen (O 2 ), nitrogen dioxide (NO 2 ), dinitrogen oxide (N 2 O), water vapor, air, hydrogen peroxide, methane, ethane, propane, butane, pentane, hexane, heptane, octane, and hydrogen sulfide.

16. The method of claim 14 , wherein the reactive gas comprises at least one of ozone (O 3 ), and oxygen (O 2 ).

17. The method of claim 14 , wherein the forming of the dielectric monolayer thin film comprising the oxide which is represented by Formula 1 and has the perovskite-type crystal structure comprises
forming a two-dimensional nanosheet monolayer including the oxide which is represented by Formula 1 and has the perovskite-type crystal structure; and
forming the dielectric monolayer thin film using the two-dimensional nanosheet monolayer.

18. The method of claim 17 , wherein the forming the two-dimensional nanosheet monolayer comprises:
obtaining a layered proton-exchange ceramic material through proton-exchange reaction of a layered ceramic material represented by Formula 4; and
intercalating an intercalation material into the layered proton-exchange ceramic material to exfoliate a nanosheet therefrom,
D[A 2 B n−3 C n O 3n+1 ]  <Formula 4>

wherein, in Formula 4, A is the divalent element, B is the monovalent element, C is the pentavalent element, n is the number from 3 to 8, and D is at least one of Li, Na, K, Rb, and Cs.

19. The method of claim 18 , wherein the intercalation material is a C1-C20 alkyl ammonium compound.

20. The method of claim 18 , wherein the layered ceramic material represented by Formula 4 is at least one of KSr 2 Nb 3 O 10 , KSr 2 NaNb 4 O 13 , KSr 2 Na 2 Nb 5 O 16 , KSr 2 NaTa 4 O 13 , KSr 2 Na 2 Ta 5 O 16 , KSr 2 KNb 4 O 13 , KSr 2 K 2 Nb 5 O 16 , KSr 2 RbNb 4 O 13 , KSr 2 Rb 2 Nb 5 O 16 , KCa 2 Nb 3 O 10 , KCa 2 NaNb 4 O 13 , KCa 2 Na 2 Nb 5 O 16 , KCa 2 KNb 4 O 13 , KCa 2 K 2 Nb 5 O 16 , KCa 2 RbNb 4 O 13 , KCa 2 Rb 2 Nb 5 O 16 , KCa 2 Ta 3 O 10 , KCa 2 NaTa 4 O 13 , KCa 2 Na 2 Ta 5 O 16 , KCa 2 KTa 4 O 13 , KCa 2 K 2 Ta 5 O 16 , KCa 2 RbTa 4 O 13 , KCa 2 Rb 2 Ta 5 O 16 , KBa 2 Nb 3 O 10 , KBa 2 NaNb 4 O 13 , KBa 2 Na 2 Nb 5 O 16 , KBa 2 KNb 4 O 13 , KBa 2 K 2 Nb 5 O 16 , KBa 2 RbNb 4 O 13 , KBa 2 Rb 2 Nb 5 O 16 , KBa 2 Ta 3 O 10 , KBa 2 NaTa 4 O 13 , KBa 2 Na 2 Ta 5 O 16 , KBa 2 KTa 4 O 13 , KBa 2 K 2 Ta 5 O 16 , KBa 2 RbTa 4 O 13 , and KBa 2 Rb 2 Ta 5 O 16 .

21. The method of claim 14 , wherein the treating with UV and the reactive gas is performed at a UV power of about 200 W to about 400 W with a UV irradiation duration of about 1 hour to about 60 hours.

22. The method of claim 14 , wherein the forming of the dielectric monolayer thin film including the oxide which is represented by Formula 1 and the perovskite-type crystal structure is performed through at least one of a chemical vapor deposition process, an organic metal chemical vapor deposition process, a liquid phase epitaxy process, a sol-gel process, a sputtering process, and a pulsed laser deposition process.

Assignees

• Samsung Electronics Co Ltd
• Nat Inst Materials Science

Inventors

• Kim Hyungjun
• Takaaki Taniguchi
• Takayoshi Sasaki
• Minoru Osada
• Kwak Chan
• Kwon Youngnam
• Lee Changsoo

Classifications

• H10D62/118

  Nanostructure semiconductor bodies · CPC title

• H10D1/696

  comprising multiple layers, e.g. comprising a barrier layer and a metal layer (barrier layers to prevent diffusion of hydrogen or oxygen in perovskite based capacitors H10D1/688) · CPC title

• H10D1/684 Primary

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

• H10P14/6328

  Deposition from the gas or vapour phase · CPC title

• H10W20/046 Primary

  the barrier, adhesion or liner layers being associated with interconnections of capacitors · CPC title