Deposition of SiN

• US 9,576,792 B2
• Filed: 09/15/2015
• Issued: 02/21/2017
• 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, Yamada, Ryoko, Pore, Viljami, Niskanen, Antti Juhani
• Primary Examiner(s): KUSUMAKAR, KAREN M
• Application Number:
  US14/855,261
• Publication Number:
  US 20160079054A1
• Time in Patent Office: 525 Days
• Field of Search: 438/762, 438765-794
• US Class Current: 1/1
• 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 substrate in a reaction space comprising:

contacting the substrate with a silicon precursor comprising iodine to provide a first silicon species adsorbed on a 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

conducting a nitrogen plasma treatment, wherein the nitrogen plasma treatment comprises contacting the substrate comprising SiN with a second plasma formed from a nitrogen containing gas substantially free of hydrogen-containing species to form the SiN thin film; and

further comprising exposing the substrate to a third plasma different from at least one of the first plasma and the second plasma.

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 first plasma is generated using a first power and the second plasma is generated using a second power.

4. The method of claim 3, wherein the second power is greater than the first power.

5. The method of claim 3, wherein the second power is less than the first power.

6. The method of claim 1, wherein contacting the substrate with the first plasma is carried out for a duration that is greater than the duration of the nitrogen plasma treatment.

7. The method of claim 6, wherein the duration of the nitrogen plasma treatment is 5% to 75% that of the duration of contacting the substrate with the first plasma.

8. The method of claim 1, further comprising repeating contacting the substrate with the silicon precursor comprising iodine and contacting the substrate with the first plasma two or more times prior to conducting the nitrogen plasma treatment.

9. The method of claim 8, wherein the nitrogen plasma treatment is conducted after at least 25 repetitions.

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

11. 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.

12. The method of claim 1, wherein the silicon precursor comprises SiI₂H₂.

13. The method of claim 1, wherein at least one of the first and third plasmas comprise a plasma generated using both hydrogen gas and nitrogen gas.

14. A method of depositing a SiN thin film on a substrate in a reaction space comprising:

exposing the substrate to a silicon precursor comprising iodine such that silicon species adsorb onto a surface of the substrate; and

exposing the substrate comprising the silicon species adsorbed onto the surface to a first nitrogen-containing plasma, and a second different plasma and

exposing the substrate to a third plasma different from at least one of the first plasma and the second plasma.

15. The method of claim 14, wherein exposing the substrate to the first nitrogen-containing plasma comprises exposing the substrate to a plasma generated using both hydrogen gas and nitrogen gas.

16. The method of claim 14, wherein two of the first, second and third plasmas comprise a plasma generated using both hydrogen gas and nitrogen gas, and one of the first, second and third plasmas comprise a plasma generated using hydrogen gas.

17. The method of claim 14, wherein the substrate is exposed to the first plasma for a first duration, the substrate is exposed to the second plasma for a second duration, and the substrate is exposed to the third plasma for a third duration, and wherein the first duration is greater than the second duration, and wherein the second duration is greater than the third duration.

18. A method of depositing a SiN thin film on a substrate in a reaction space, comprising:

exposing the substrate to a silicon halide such that silicon species adsorb onto a surface of the substrate;

exposing the substrate to a first plasma generated using nitrogen-containing and hydrogen-containing gas;

exposing the substrate to a second plasma generated using hydrogen-containing gas;

exposing the substrate to a third plasma generated using hydrogen-containing gas and nitrogen-containing gas; and

repeating exposing the substrate to the silicon halide, and the first plasma, the second plasma and the third plasma.

19. The method of claim 18, further comprising:

removing excess reactants from the reaction space between exposing the substrate to the first plasma and the second plasma, and

removing excess reactants from the reaction space between exposing the substrate to the second plasma and the third plasma.

20. The method of claim 18, wherein removing excess reactants comprises turning off the plasma and flowing hydrogen gas.

21. The method of claim 20, wherein no additional reactants are used for depositing the thin film.

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

depositing SiN on the substrate using an atomic layer deposition process, wherein the atomic layer deposition process comprises;

contacting the substrate with a silicon precursor comprising iodine; and

subsequently contacting the substrate with a first plasma; and

conducting a nitrogen plasma treatment upon the deposited SiN, wherein the nitrogen plasma treatment comprises contacting the substrate comprising the SiN with a second plasma formed from a nitrogen containing gas and substantially free of hydrogen-containing species; and

exposing the substrate to a third plasma different from at least one of the first plasma and the second plasma.

23. The method of claim 22, wherein conducting the nitrogen plasma treatment comprises contacting the SiN on the substrate with a plasma substantially free of hydrogen-containing species.

24. The method of claim 22, wherein

the first plasma comprises activated hydrogen species.

25. The method of claim 22, further comprising repeating contacting the substrate with the silicon precursor and the first plasma two or more times prior to conducting the nitrogen plasma treatment.

26. The method of claim 24, wherein the activated hydrogen species comprises at least one of hydrogen, hydrogen atoms, hydrogen plasma, hydrogen radicals, N* radicals, NH* radicals and NH₂* radicals.

27. The method of claim 22, wherein depositing the SiN comprises generating the first plasma using a first power and wherein conducting the nitrogen plasma treatment comprises generating the nitrogen plasma using a second power, wherein the second power is greater than the first power.

28. The method of claim 22, wherein at least one of the first and third plasmas comprise a plasma generated using both hydrogen gas and nitrogen gas.