Method of atomic layer etching using functional group-containing fluorocarbon

• US 9,735,024 B2
• Filed: 12/28/2015
• Issued: 08/15/2017
• Est. Priority Date: 12/28/2015
• 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
• Primary Examiner(s): Tran, Binh X
• Application Number:
  US14/981,468
• Publication Number:
  US 20170186621A1
• Time in Patent Office: 596 Days
• Field of Search: 438694, 438722, 438723, 438724, 438742
• CPC Class Codes: H01J 37/32146 Amplitude modulation, includes pulsing
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• 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
• CPC Class Codes: H01L 21/32137 of silicon-containing layers
• CPC Class Codes: H01L 21/67069 for drying etching

Abstract

A method of atomic layer etching (ALE) uses a cycle including: continuously providing a noble gas; providing a pulse of an etchant gas to the reaction space to chemisorb the etchant gas in an unexcited state in a self-limiting manner on a surface of a substrate in the reaction space; and providing a pulse of a reactive species of a noble gas in the reaction space to contact the etchant gas-chemisorbed surface of the substrate with the reactive species so that the layer on the substrate is etched. The etchant gas is a fluorocarbon gas containing a functional group with a polarity.

Claims

1. A method for etching a layer on a substrate placed in a reaction space by an atomic layer etching (ALE) process which comprises at least one etching cycle, wherein an etching cycle comprises:

continuously providing a noble gas in the reaction space;

providing a pulse of an etchant gas in the reaction space to chemisorb the etchant gas in an unexcited state on a surface of the substrate in a self-limiting manner, said etchant gas being a fluorocarbon gas containing a functional group with a polarity, said surface of the substrate being constituted by an oxide mineral or nitride mineral; and

providing a pulse of a reactive species of a noble gas in the reaction space to contact the etchant gas-chemisorbed surface of the substrate with the reactive species so that the surface of the layer on the substrate is etched.

2. The method according to claim 1, wherein while providing the reactive species of the noble gas, no reactive species of O₂, H₂, or N₂ are present in the reaction space.

3. The method according to claim 1, wherein the pulse of the reactive species of the noble gas is provided by applying a pulse of RF power discharge between electrodes disposed in the reaction space, between which the substrate is placed.

4. The method according to claim 1, wherein the oxide or nitride mineral constituting the surface of the substrate is selected from the group consisting of SiO₂, SiON, SiN, TiO, TiON, and TiN.

5. The method according to claim 1, wherein the noble gas continuously provided in the reaction space is provided as a carrier gas for the etchant gas.

6. The method according to claim 1, wherein a purging period is taken between the pulse of the etchant gas and the pulse of the reactive species of the noble gas to remove excess etchant gas from the reaction space, and a purging period is taken after the pulse of the reactive species of the noble gas to remove by-products from the reaction space.

7. The method according to claim 1, wherein no gas other than the etchant gas flows as an etchant gas throughout the ALE process.

8. The method according to claim 1, wherein the layer of the substrate has a recess pattern.

9. The method according to claim 1, wherein the etched layer of the substrate has a conformality of 80% to 120% when the ALE process is complete.

10. The method according to claim 1, wherein the functional group contained in the etchant gas is selected from the group consisting of a hydroxyl group, amino group, ether group, ketone group, and carboxyl group.

11. The method according to claim 10, wherein the etchant gas is a perfluorocarbon-derivative gas.

12. The method according to claim 11, wherein the etchant gas is CF₃ROH, C₃F₇ROH, C₃F₇RNH₂, and/or (CF₃R)₂O wherein R represents an alkylene group having one to four carbon atoms.

13. The method according to claim 1, further comprising, prior to the ALE process, depositing a film on a substrate in the reaction space by atomic layer deposition (ALD), said film on the substrate constituting the surface of the substrate subjected to the ALE process, wherein the ALD process and the ALE process are conducted continuously in the reaction space.

14. The method according to claim 13, wherein the reaction space is controlled at a constant pressure throughout the ALD process and the ALE process.