Deposition of SiN

• US 10,262,854 B2
• Filed: 09/15/2017
• Issued: 04/16/2019
• Est. Priority Date: 09/17/2014
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM IP Holding B.V. (ASM International NV)
• Inventors: Chen, Shang, Pore, Viljami, Yamada, Ryoko, Niskanen, Antti Juhani
• Primary Examiner(s): Kusumakar, Karen
• Application Number:
  US15/706,435
• Publication Number:
  US 20180068844A1
• Time in Patent Office: 578 Days
• CPC Class Codes: C23C 16/045 Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
• CPC Class Codes: C23C 16/345 Silicon nitride
• CPC Class Codes: C23C 16/45536 Use of plasma, radiation or electromagnetic fields
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: H01L 21/0217 the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz H01L21/02126 and H01L21/0214 take precedence
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD

Abstract

Methods and precursors for forming silicon nitride films are provided. In some embodiments, silicon nitride can be deposited by atomic layer deposition (ALD), such as plasma enhanced ALD. In some embodiments, deposited silicon nitride can be treated with a plasma treatment. The plasma treatment can be a nitrogen plasma treatment. In some embodiments the silicon precursors for depositing the silicon nitride comprise an iodine ligand. The silicon nitride films may have a relatively uniform etch rate for both vertical and the horizontal portions when deposited onto three-dimensional structures such as FinFETS or other types of multiple gate FETs. In some embodiments, various silicon nitride films of the present disclosure have an etch rate of less than half the thermal oxide removal rate with diluted HF (0.5%). In some embodiments, a method for depositing silicon nitride films comprises a multi-step plasma treatment.

Claims

1. A method of forming a SiN thin film on a surface of a substrate in a reaction space comprising:

contacting the substrate with a silicon precursor comprising SiI₂H₂ to provide a first silicon species adsorbed on the surface of the substrate;

contacting the substrate comprising the first silicon species adsorbed on the surface with a first plasma comprising activated hydrogen species thereby forming SiN on the substrate; and

contacting the substrate comprising SiN with a second plasma formed from a nitrogen containing gas, wherein the first plasma is generated using a first power and the second plasma is generated using a second power that is different from the first power.

2. The method of claim 1, wherein the first plasma comprises at least one of hydrogen, hydrogen atoms, hydrogen plasma, hydrogen radicals, N* radicals, NH* radicals and NH₂* radicals.

3. The method of claim 1, wherein the second plasma is formed from a nitrogen containing gas that is substantially free of hydrogen-containing species.

4. The method of claim 1, wherein the second power is greater than the first power.

5. The method of claim 4, wherein the second power is up to 900% of the first power.

6. The method of claim 1, wherein the second power is less than the first power.

7. The method of claim 1, wherein the second power is between 50% and 100% of the first power.

8. The method of claim 1, wherein the first power is from 50 W to 600 W.

9. The method of claim 1, wherein the second power is from 100 W to 1000 W.

10. The method of claim 1, wherein the first plasma has a plasma energy of less than 2500 W*s.

11. The method of claim 1, wherein the second plasma has a power density of about 0.07 W/Cm³ to about 70 W/cm³.

12. The method of claim 1, wherein the substrate is contacted with the first plasma for a first duration and contacted with the second plasma for a second duration that is less than the first duration.

13. The method of claim 12, wherein the second duration is 5% to 75% of the first duration.

14. The method of claim 1, further comprising repeating contacting the substrate with the silicon precursor comprising SiI₂H₂ and contacting the substrate with the first plasma two or more times prior to contacting the substrate with the second plasma.

15. The method of claim 14, wherein the substrate is contacted with the second plasma after at least 25 repetitions.

16. The method of claim 14, wherein a total duration during which the substrate is contacted with the first plasma is greater than or equal to a total duration during which the substrate is contacted with the second plasma.

17. The method of claim 1, further comprising exposing the substrate to a third plasma different from at least one of the first plasma and the second plasma.

18. The method of claim 1, wherein the SiN thin film is formed on a three-dimensional structure comprising a sidewall and a top region and wherein a ratio of a wet etch rate (WER) of the SiN thin film on the sidewall to a wet etch rate (WER) of the SiN thin film on the top region is from 0.75 to 1.5 in 0.5% dHF.

19. The method of claim 1, wherein an etch rate ratio of an etch rate of the SiN thin film to an etch rate of a thermal silicon oxide film is less than 0.5 in 0.5% aqueous HF.