Atomic Layer Deposition Of Films Comprising Si(C)N Using Hydrazine, Azide And/Or Silyl Amine Derivatives

• US 20140273526A1
• Filed: 03/12/2014
• Published: 09/18/2014
• Est. Priority Date: 03/12/2013
• Status: Abandoned Application

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Thompson, David
• Application Number:
  US14/205,921
• Publication Number:
  US 20140273526A1
• Time in Patent Office: Days
• US Class Current: 438/786
• CPC Class Codes: C23C 16/36 Carbonitrides
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: H01L 21/02167 the material being a silicon carbide not containing oxygen, e.g. SiC, SiC:H or silicon carbonitrides 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 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD

Abstract

Provided are methods for the deposition of films comprising Si(C)N via atomic layer deposition processes. The methods include exposure of a substrate surface to a silicon precursor and a co-reagent comprising a compound selected from the group consisting of N═N═N—R, R₂N—NR₂, and (R₃Si)_qNH_3-q, wherein q has a value of between 1 and 3, and each R is independently selected from organosilicons, C1-C6 substituted or un-substituted alkanes, branched or un-branched alkanes, substituted or un-substituted alkenes, branched or un-branched alkenes, substituted or un-substituted alkynes, branched or un-branched alkynes or substituted or un-substituted aromatics.

Claims

1. A method of depositing a film comprising Si(C)N, the method comprising exposing a substrate surface to a silicon precursor and a co-reactant, wherein the silicon precursor contains at least one Si—

X bond, wherein X is a halogen, and the co-reactant comprises a compound selected from the group consisting of N═

N═

N—

R, R₂N—

NR₂, and (R₃Si)_qNH_3-q, wherein q has a value of between 1 and 3, and each R is independently selected from silyl, monomethyl silyl, dimethyl silyl and trimethyl silyl, C1-C6 substituted or un-substituted alkanes, branched or un-branched alkanes, substituted or un-substituted alkenes, branched or un-branched alkenes, substituted or un-substituted alkynes, branched or un-branched alkynes or substituted or un-substituted aromatics.

2. The method of claim 1, wherein each R is independently C1-C6 alkyl.

3. The method of claim 2, wherein each R is methyl.

4. The method of claim 1, wherein the co-reactant comprises (R₃Si)_qNH_3-q.

5. The method of claim 1, wherein the co-reactant comprises N-methylhydrazine, 1,1-dimethylhydrazine, or 1,1,2,2-tetramethylhydrazine.

6. The method of claim 1, wherein the co-reactant comprises trimethylsilylazide.

7. The method of claim 1, wherein the silicon precursor has formula (X_yH_3-ySi)_zCl_4-z, (X_yH_3-ySi)(CH₂)(SiX_pH_2-p)(CH₂) (SiX_yH_3-y), or (X_yH_3-ySi)(CH₂)_n(SiX_yH_3-y), wherein X is a halogen selected from Cl, Br and I, y has a value of between 1 and 3, z has a value of between 1 and 3, p has a value of between 0 and 2, and n has a value between 2 and 5.

8. The method of claim 1, wherein the silicon precursor has a formula (X_yH_3-ySi)_zCH_4-z.

9. The method of claim 8, wherein the silicon precursor has a formula (X_yH_3-ySi)(CH₂)_n(SiX_yH_3-y), wherein X is a halogen selected from Cl, Br and I, y has a value of between 1 and 3, and n has a value between 2 and 5.

10. The method of claim 1, wherein the silicon precursor comprises SiH_4-rX_r or H_3-tX_tSi—

SiH_3-tX_t, wherein each X is a halogen, r has a value of 1 to 4, and t has a value of 1 to 3.

11. The method of claim 10, wherein the silicon precursor comprises monochlorosilane.

12. The method of claim 1, wherein the silicon precursor or the co-reactant comprises carbon, and a film comprising silicon carbonitride is provided.

13. The method of claim 1, wherein a film comprising silicon nitride is provided.

14. A method of plasma enhanced atomic layer deposition of a film comprising Si(C)N, the method comprising

a. exposing a substrate surface to a silicon precursor, wherein the silicon precursor contains at least one Si—

X bond, wherein X is a halogen; and

b. subsequently exposing a substrate to a co-reactant and striking a plasma, wherein the co-reactant comprises a compound selected from the group consisting of N═

N═

N—

R and R₂N—

NR₂, wherein q has a value of between 1 and 3, and each R is independently selected from C1-C6 substituted or un-substituted alkanes, branched or un-branched alkanes, substituted or un-substituted alkenes, branched or un-branched alkenes, substituted or un-substituted alkynes, branched or un-branched alkynes or substituted or un-substituted aromatics.

15. The method of claim 14, wherein each R is C1-C6 alkyl.

16. The method of claim 15, wherein each R is methyl.

17. The method of claim 14, wherein the co-reactant comprises N-methylhydrazine, 1,1-dimethylhydrazine, or 1,1,2,2-tetramethylhydrazine.

18. The method of claim 14, wherein the substrate has a temperature of about 50 to about 250°

C.

19. The method of claim 114, wherein the silicon precursor comprises monochlorosilane.

20. A method of depositing a film comprising Si(C)N, the method comprising exposing a substrate surface to hexachlorodisilane, dichlorosilane or monochlorosilane, wherein X is a halogen, and the co-reactant comprises a compound selected from the group consisting of N═

N═

N—

R, R₂N—

NR₂, and (R₃Si)_qNH_3-q, wherein q has a value of between 1 and 3, and each R is independently C1-C6 alkyl.