Low Temperature Deposition of Silicon-Containing Films

• US 20100304047A1
• Filed: 06/02/2009
• Published: 12/02/2010
• Est. Priority Date: 06/02/2008
• Status: Active Grant

• Current Assignee: Tokyo Electron Limited, Versum Materials US Inc.
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc), Tokyo Electron Limited
• Inventors: Yonezawa, Masato, Matsunaga, Masanobu, Han, Bing, Hasebe, Kazuhide, Xiao, Manchao, Lei, Xinjian, Yang, Liu, Cheng, Hansong, Karwacki, Eugene Joseph JR.
• Granted Patent: US 8,298,628 B2
• Time in Patent Office: Days
• US Class Current: 427/577
• CPC Class Codes: C23C 16/308 Oxynitrides
• CPC Class Codes: C23C 16/345 Silicon nitride
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/45536 Use of plasma, radiation or electromagnetic fields
• CPC Class Codes: H01L 21/02126 the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
• CPC Class Codes: H01L 21/0214 the material being a silicon oxynitride, e.g. SiON or SiON:H
• CPC Class Codes: H01L 21/02164 the material being a silicon oxide, e.g. SiO2
• 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 21/02271 deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition H01L21/02266 takes 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
• CPC Class Codes: H01L 21/3145 formed by deposition from a gas or vapour
• CPC Class Codes: H01L 21/31608 Deposition of SiO2 H01L21/31625, H01L21/31629 and H01L21/31633 take precedence
• CPC Class Codes: H01L 21/31633 Deposition of carbon doped silicon oxide, e.g. SiOC
• CPC Class Codes: H01L 21/3185 of siliconnitrides

Abstract

This invention discloses the method of forming silicon nitride, silicon oxynitride, silicon oxide, carbon-doped silicon nitride, carbon-doped silicon oxide and carbon-doped oxynitride films at low deposition temperatures. The silicon containing precursors used for the deposition are monochlorosilane (MCS) and monochloroalkylsilanes. The method is preferably carried out by using plasma enhanced atomic layer deposition, plasma enhanced chemical vapor deposition, and plasma enhanced cyclic chemical vapor deposition.

Claims

1. A process to deposit silicon nitride or carbon-doped silicon nitride on a substrate in a processing chamber, comprising:

a. contacting the substrate with a nitrogen-containing source to absorb at least a portion of the nitrogen-containing source on the substrate;

b. purging unabsorbed nitrogen-containing source;

c. contacting the substrate with a silicon-containing precursor to react with the portion of the absorbed nitrogen-containing source; and

d. purging unreacted silicon-containing source;

wherein the process is a plasma-enhanced process.

2. The process to deposit silicon nitride of claim 1 wherein the silicon-containing source is monochlorosilane.

3. The process to deposit carbon-doped silicon nitride of claim 1 wherein the silicon-containing source is monochloroalkylsilane having a general formula of ClSiH_xR¹_nR²_m-x wherein x=1, 2;

m=1, 2, 3;

n=0, 1, n+m=<

3;

R¹ and R² are linear, branched or cyclic independently selected from the group consisting of alkyl, alkenyl, alkynyl, and aryl having 1-10 carbon atoms.

4. The silicon-containing source in claim 3 is selected from the group consisting of ClSiEtH₂, ClSiEt₂H, ClSi(CH═

CH₂)H₂, ClSi(CH═

CH₂)MeH, ClSi(CH═

CH₂)EtH, ClSi(CCH)H₂, ClSi(iso-Pr)₂H, ClSi(sec-Bu)₂H, ClSi(tert-Bu)₂H, ClSi(iso-Pr)H₂, ClSi(sec-Bu)H₂, ClSi(tert-Bu)H₂, and mixtures thereof.

5. The process of claim 1 is selected from the group consisting of plasma enhanced atomic layer deposition, and plasma enhanced cyclic chemical vapor deposition;

wherein the plasma is selected from the group consisting of an ammonia plasma, a nitrogen plasma, a mixture of nitrogen and hydrogen plasma, and a mixture of nitrogen and argon plasma;

plasma-excited silicon precursor is optional.

6. The process of claim 5, wherein the plasma is an in-situ generated plasma or a remotely generated plasma.

7. The process of claim 1 wherein the nitrogen-containing source for depositing silicon nitride is selected from the group consisting of nitrogen, ammonia, hydrazine, monoalkylhydrozine, dialkylhydrozine, and mixture thereof;

and the nitrogen-containing source for depositing carbon-doped silicon nitride is selected from the group consisting of nitrogen, ammonia, hydrazine, monoalkylhydrozine, dialkylhydrozine, hydroxylamine (NH₂OH), tert-butylamine (NH₂C(CH₃)₃), allylamine (NH₂CH₂CHCH₂), hydroxylamine hydrochloride, methylamine, diethylamine, triethylamine and mixture thereof.

8. A process to deposit silicon oxide or carbon-doped silicon oxide on a substrate in a processing chamber, comprising:

a. contacting the substrate with an oxygen-containing source to absorb at least a portion of the oxygen-containing source on the substrate;

b. purging unabsorbed oxygen-containing source;

c. contacting the substrate with a silicon-containing precursor to react with the portion of the absorbed oxygen-containing source; and

d. purging unreacted silicon-containing source.

9. The process to deposit silicon oxide of claim 8 wherein the silicon-containing source is monochlorosilane.

10. The process to deposit carbon-doped silicon oxide of claim 8 wherein the silicon-containing source is monochloroalkylsilane having a general formula of ClSiH_xR¹_nR²_m-x wherein x=1, 2;

m=1, 2, 3;

n=0, 1, n+m=<

3;

R¹ and R² are linear, branched or cyclic independently selected from the group consisting of alkyl, alkenyl, alkynyl, and aryl having 1-10 carbon atoms.

11. The silicon-containing source in claim 10 is selected from the group consisting of ClSiEtH₂, ClSiEt₂H, ClSi(CH═

CH₂)H₂, ClSi(CH═

CH₂)MeH, ClSi(CH═

CH₂)EtH, ClSi(CCH)H₂, ClSi(iso-Pr)₂H, ClSi(sec-Bu)₂H, ClSi(tert-Bu)₂H, ClSi(iso-Pr)H₂, ClSi(sec-Bu)H₂, ClSi(tert-Bu)H₂, and mixtures thereof.

12. The process of claim 8 is selected from the group consisting of plasma enhanced atomic layer deposition, plasma enhanced chemical vapor deposition and plasma enhanced cyclic chemical vapor deposition.

13. The process of claim 12, wherein the plasma is an in-situ generated plasma or a remotely generated plasma.

14. The process of claim 8 wherein the oxygen-containing source is selected from the group consisting of oxygen, water, nitrous oxide, ozone, and mixture thereof.

15. A process to deposit silicon oxynitride or carbon-doped silicon oxynitride on a substrate in a processing chamber, comprising:

a. contacting the substrate with a mixture of an oxygen-containing source and a nitrogen-containing source to absorb at least a portion of the oxygen-containing source and at least a portion of the nitrogen-containing source on the substrate;

b. purging unabsorbed oxygen-containing source and nitrogen-containing source;

c. contacting the substrate with a silicon-containing precursor to react with the portion of the absorbed oxygen-containing source and nitrogen-containing source; and

d. purging unreacted silicon-containing source.

16. The process deposit silicon oxynitride of claim 15 wherein the silicon-containing source is monochlorosilane.

17. The process deposit carbon-doped silicon oxynitride of claim 15 wherein the silicon-containing source is monochloroalkylsilane having a general formula of ClSiH_xR¹_nR²_m-x wherein x=1, 2;

m=1, 2, 3;

n=0, 1, n+m=<

3;

R¹ and R² are linear, branched or cyclic independently selected from the group consisting of alkyl, alkenyl, alkynyl, and aryl having 1-10 carbon atoms.

18. The silicon-containing source in claim 17 is selected from the group consisting of ClSiEtH₂, ClSiEt₂H, ClSi(CH═

CH₂)H₂, ClSi(CH═

CH₂)MeH, ClSi(CH═

CH₂)EtH, ClSi(CCH)H₂, ClSi(iso-Pr)₂H, ClSi(sec-Bu)₂H, ClSi(tert-Bu)₂H, ClSi(iso-Pr)H₂, ClSi(sec-Bu)H₂, ClSi(tert-Bu)H₂, and mixtures thereof.

19. The process of claim 15 is selected from the group consisting of plasma enhanced atomic layer deposition, plasma enhanced chemical vapor deposition and plasma enhanced cyclic chemical vapor deposition.

20. The process of claim 19, wherein the plasma is an in-situ generated plasma or a remotely generated plasma.

21. The process of claim 15 wherein the oxygen-containing source is selected from the group consisting of oxygen, water, nitrous oxide, ozone, and mixture thereof.

22. The process of claim 15 wherein the nitrogen-containing source is selected from the group consisting of nitrogen, ammonia, hydrazine, monoalkylhydrozine, dialkylhydrozine, hydroxylamine (NH₂OH), tert-butylamine (NH₂C(CH₃)₃), allylamine (NH₂CH₂CHCH₂), hydroxylamine hydrochloride, methylamine, diethylamine, triethylamine and mixture thereof.