Method of forming conformal dielectric film having Si-N bonds by PECVD

• US 7,972,980 B2
• Filed: 05/12/2010
• Issued: 07/05/2011
• Est. Priority Date: 01/21/2009
• Status: Active Grant

• Current Assignee: ASM Japan K.K. (ASM International NV)
• Original Assignee: ASM Japan K.K. (ASM International NV)
• Inventors: Lee, Woo Jin, Shimizu, Akira
• Primary Examiner(s): Smith; Matthew
• Assistant Examiner(s): Baptiste; Wilner Jean
• Application Number:
  US12/778,808
• Publication Number:
  US 20100221925A1
• Time in Patent Office: 419 Days
• Field of Search: 438/792, 438/791, 438/723, 438/712, 438/710, 257/E21.487
• US Class Current: 438/792
• 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 16/45523 Pulsed gas flow or change of composition over time
• 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 21/02211 the compound being a silane, e.g. disilane, methylsilane or chlorosilane
• CPC Class Codes: H01L 21/02219 the compound comprising silicon and nitrogen
• 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
• CPC Class Codes: H01L 21/31604 Deposition from a gas or vapour H01L21/31691, H01L21/31695 take precedence
• CPC Class Codes: H01L 21/3185 of siliconnitrides

Abstract

A method of forming a conformal dielectric film having Si—N bonds on a semiconductor substrate by plasma enhanced chemical vapor deposition (PECVD) includes: introducing a nitrogen- and hydrogen-containing reactive gas and a rare gas into a reaction space inside which a semiconductor substrate is placed; applying RF power to the reaction space; and introducing a hydrogen-containing silicon precursor as a first precursor and a hydrocarbon gas as a second precursor in pulses into the reaction space wherein a plasma is excited, thereby forming a conformal dielectric film doped with carbon and having Si—N bonds on the substrate.

Claims

1. A method of forming a conformal dielectric film having Si—

N bonds on a semiconductor substrate by plasma enhanced chemical vapor deposition (PECVD), which comprises;

introducing a nitrogen- and/or hydrogen-containing reactive gas and a rare gas into a reaction space inside which the semiconductor substrate is placed;

applying RF power to the reaction space; and

introducing a hydrogen-containing silicon gas as a first precursor and a hydrocarbon gas as a second precursor separately, each precursor being introduced in pulses of less than 5-second duration into the reaction space while introducing the reactive gas and the rare gas and exciting a plasma without interruption, thereby forming a conformal dielectric film having Si—

N bonds on the substrate.

2. The method according to claim 1, wherein the first precursor has a formula of Si_α

H_β

X_γ

, wherein α

, β and

γ

are integers (γ

includes zero), wherein X comprises N, F and/or C_mH_n, wherein m and n are integers.

3. The method according to claim 1, wherein the first precursor is a liquid at room temperature and vaporized upstream of the reaction space.

4. The method according to claim 1, wherein the first precursor is introduced in pulses while the reactive gas and the rare gas are continuously introduced and the RF power is continuously applied.

5. The method according to claim 1, wherein the pulse duration of the first precursor is equal to or shorter than the interval between pulses.

6. The method according to claim 5, wherein the first precursor is introduced in pulses of a duration of approximately 0.1 sec to 1.0 sec with an interval between pulses of approximately 0.1 sec to 3.0 sec.

7. The method according to claim 1, wherein the rare gas comprises at least one of a mixture of N₂ and H₂, a mixture of NH₃ and H₂, and a nitrogen-boron-hydrogen gas.

8. The method according to claim 1, wherein the rare gas comprises a mixture of helium and argon or a mixture of helium and krypton.

9. The method according to claim 1, wherein the conformal dielectric film is a carbon-doped silicon nitride film having a carbon concentration of about 5% to about 40% and a conformality of about 80% or higher.

10. The method according to claim 1, wherein the first precursor has no carbon atom in its molecule, and the second precursor has no silicon atom in its molecule.

11. The method according to claim 10, wherein the first precursor and the second precursor are introduced in pulses having the same cycle.

12. The method according to claim 10, wherein the first precursor and the second precursor are introduced in pulses having different cycles, wherein more than one cycle of the second precursor is performed per one cycle of the first precursor.

13. The method according to claim 11, wherein the pulse duration of the second precursor is one to ten times longer than that of the first precursor.

14. The method according to claim 1, wherein the second precursor is selected from the group consisting of CH₄, C₂H₆, C₅H₁₂, and C₆H₁₄.

15. The method according to claim 1, wherein the gases introduced into the reaction space consist of the first precursor, the second precursor, the reactive gas, and the rare gas.

16. A method of forming a conformal dielectric film having Si—

N bonds on a semiconductor substrate by plasma enhanced chemical vapor deposition (PECVD), which comprises;

introducing a nitrogen- and/or hydrogen-containing reactive gas and a rare gas into a reaction space inside which the semiconductor substrate is placed;

applying RF power to the reaction space; and

introducing a hydrogen-containing silicon gas as a first precursor and a hydrocarbon gas as a second precursor separately, each precursor being introduced in pulses of less than 5-second duration into the reaction space while introducing the reactive gas and the rare gas and exciting a plasma without interruption, thereby forming a conformal dielectric film having Si—

N bonds on the substrate; and

after forming the conformal dielectric film as a first conformal dielectric film, increasing the pulse duration of the second precursor per cycle without changing the length of one cycle which is the same as that for the first precursor, or performing multiple cycles of the second precursor per one cycle of the first precursor, thereby forming a second conformal dielectric film which has a carbon concentration higher than that of the first conformal dielectric film.

17. A method of forming dielectric films having Si—

N bonds on a semiconductor substrate by plasma enhanced chemical vapor deposition (PECVD), which comprises;

(i) introducing a nitrogen- and/or hydrogen-containing reactive gas and an rare gas into a reaction space inside which the semiconductor substrate is placed;

(ii) applying RF power to the reaction space;

(iii) introducing as a first precursor a hydrogen-containing silicon gas in pulses of less than a 5-second duration into the reaction space while introducing the reactive gas and the inert gas and exciting a plasma without interruption, thereby forming a first dielectric film having Si—

N bonds on the substrate; and

(iv) forming a second dielectric film having Si—

N bonds on the substrate by repeating steps (i) to (iii), wherein step (iii) further comprises introducing a second precursor in pulses while introducing the first precursor in pulses at the same timing, thereby increasing wet etching resistance of the second dielectric film as compared with that of the first dielectric film, said second precursor being a hydrocarbon gas containing no silicon.

18. The method according to claim 17, wherein step (iv) further comprises prolonging the pulse duration of the second precursor relative to that of the first precursor.

19. The method according to claim 18, wherein the pulse duration of the second precursor is at least four times longer than that of the first precursor.

20. The method according to claim 17, wherein step (iv) further comprises reducing nitrogen gas flow relative to that for the first dielectric film, and/or increasing the number of cycles of the second precursor per cycle of the first precursor.