Method of atomic layer etching using hydrogen plasma

• US 10,504,742 B2
• Filed: 05/23/2018
• Issued: 12/10/2019
• Est. Priority Date: 05/31/2017
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM IP Holding B.V. (ASM International NV)
• Inventors: Zaitsu, Masaru, Kobayashi, Nobuyoshi, Kobayashi, Akiko, Hori, Masaru, Tsutsumi, Takayoshi
• Primary Examiner(s): Vinh, Lan
• Application Number:
  US15/987,755
• Publication Number:
  US 20180350620A1
• Time in Patent Office: 566 Days
• Field of Search: 438706, 438710, 438712, 438714, 438719, 438723, 438736, 438765, 438780
• CPC Class Codes: H01L 21/02112 characterised by the material of the layer
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/30621 Vapour phase etching
• CPC Class Codes: H01L 21/3065 Plasma etching; Reactive-ion etching
• CPC Class Codes: H01L 21/31116 by dry-etching
• CPC Class Codes: H01L 21/31122 of layers not containing Si, e.g. PZT, Al2O3
• CPC Class Codes: H01L 21/32136 using plasmas

Abstract

A method for etching a target layer on a substrate by a dry etching process includes at least one etching cycle, wherein an etching cycle includes: depositing a carbon halide film using reactive species on the target layer on the substrate; and etching the carbon halide film using a plasma of a non-halogen hydrogen-containing etching gas, which plasma alone does not substantially etch the target layer, thereby generating a hydrogen halide as etchant species at a boundary region of the carbon halide film and the target layer, thereby etching a portion of the target layer in the boundary region.

Claims

1. A method for etching a target layer on a substrate by a dry etching process which comprises at least one etching cycle, wherein an etching cycle comprises:

(i) depositing a carbon halide film using reactive species on the target layer on the substrate, wherein the carbon halide film and the target layer are in contact with each other; and

(ii) etching the carbon halide film using a plasma of a non-halogen hydrogen-containing etching gas without etching the target layer, which plasma alone does not substantially etch the target layer, wherein a hydrogen halide is generated as a by-product of the etching of the carbon halide film as etchant species at a boundary region of the carbon halide film and the target layer, thereby chemically etching a portion of the target layer in the boundary region without a plasma other than the plasma of the non-halogen hydrogen-containing etching gas.

2. The method according to claim 1, wherein step (ii) continues until the carbon halide film is substantially entirely etched, indicating that substantially the entire portion of the boundary region of the target layer is etched.

3. The method according to claim 1, wherein a duration of step (i) is correlated with a thickness of the etched portion of the target layer until the thickness of the etched portion of the target layer reaches a plateau while the duration of step (i) increases, and step (i) continues until the thickness of the etched portion of the target layer reaches the plateau or a point near the plateau.

4. The method according to claim 1, wherein the etching cycle is repeated at least two times.

5. The method according to claim 1, wherein step (i) continues until a thickness of the carbon halide film falls within a range of 0.5 nm to 10 nm.

6. The method according to claim 1, wherein in step (ii), a thickness of the etched portion of the target layer is 0.1 nm to 2.0 nm.

7. The method according to claim 1, wherein in step (i), the carbon halide film is deposited by a gas phase reaction wherein the reactive species are those of an etchant gas or gases constituted by a halogen and a carbon.

8. The method according to claim 7, wherein the halogen is F or Cl.

9. The method according to claim 8, wherein the halogen is F, and the etchant species is HF.

10. The method according to claim 8, wherein the etchant gas is CxFy having a double or triple bond wherein x and y are integers and x is at least 2.

11. The method according to claim 7, wherein the gas phase reaction is plasma-enhanced CVD.

12. The method according to claim 11, wherein the plasma-enhanced CVD comprises:

(a) continuously feeding a noble gas to a reaction space wherein the substrate is placed;

(b) continuously feeding a carbon halide gas to the reaction space; and

(c) after elapse of a preset duration of steps (a) and (b) without excitation of the noble gas and the carbon halide gas, applying RF power to the reaction space to deposit the carbon halide film on the target layer, wherein no oxidizing gas is fed to the reaction space throughout steps (a) through (c).

13. The method according to claim 12, wherein a duration of step (c) is shorter than the preset duration of steps (a) and (b).

14. The method according to claim 1, wherein in step (ii), the non-halogen hydrogen-containing etching gas is hydrogen or ammonia or a mixture of hydrogen or ammonia and a rare gas and contains no oxygen.

15. The method according to claim 1, wherein in step (ii), the carbon halide film is etched by reactive ion etching (RIE).

16. The method according to claim 15, wherein the RIE is capacitively-coupled plasma etching.

17. The method according to claim 16, wherein the capacitively-coupled plasma etching comprises:

(a) continuously feeding a reactant gas to a reaction space wherein the substrate is placed; and

(b) after elapse of a preset duration of step (a) without excitation of the reactant gas, applying RF power to the reaction space to etch the carbon halide film and the target layer.

18. The method according to claim 1, wherein the target layer is constituted by SiO₂, metal oxide, or a metal, which is etchable by a hydrogen halide.

19. The method according to claim 1, wherein step (i) and step (ii) are continuously conducted in the same reaction chamber.