AZA-polysilane precursors and methods for depositing films comprising same

• US 9,796,739 B2
• Filed: 06/02/2014
• Issued: 10/24/2017
• Est. Priority Date: 06/26/2013
• Status: Active Grant

• Current Assignee: Versum Materials US Inc.
• Original Assignee: Versum Materials US Inc.
• Inventors: Xiao, Manchao, Lei, Xinjian, Spence, Daniel P.
• Primary Examiner(s): MILLER, JR, JOSEPH ALBERT
• Application Number:
  US14/293,554
• Publication Number:
  US 20150147871A1
• Time in Patent Office: 1,240 Days
• Field of Search: None
• CPC Class Codes: C07F 7/025 without C-silicon linkages
• CPC Class Codes: C07F 7/10 containing nitrogen having a Si-N linkage
• CPC Class Codes: C07F 7/21 Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
• CPC Class Codes: C23C 16/24 Deposition of silicon only
• CPC Class Codes: C23C 16/345 Silicon nitride
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/45544 characterized by the apparatus
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• 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 21/02164 the material being a silicon oxide, e.g. SiO2
• 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 21/0217 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
• CPC Class Codes: H01L 21/02532 Silicon, silicon germanium, germanium
• CPC Class Codes: H01L 21/02592 amorphous
• CPC Class Codes: H01L 21/0262 Reduction or decomposition of gaseous compounds, e.g. CVD

Abstract

Described herein are precursors and methods for forming silicon-containing films. In one aspect, there is provided an aza-polysilane precursor comprising at least two Si—N bonds, at least one Si—Si bond, and at least two SiH₂ groups represented by the following Formula IA, IB and IC:

wherein R¹ and R² are independently selected from a linear or branched C₁ to C₁₀ alkyl group, a linear or branched C₃ to C₁₀ alkenyl group, a linear or branched C₃ to C₁₀ alkynyl group, C₃ to C₁₀ cyclic alkyl group, C₃ to C₁₀ hetero-cyclic alkyl group, a C₅ to C₁₀ aryl group, and a C₃ to C₁₀ hetero-aryl group, a C₂ to C₁₀ dialkylamino group, a C₃ to C₁₀ cyclic alkylamino group; R³ and R⁴ are independently selected from hydrogen, a linear or branched C₁ to C₁₀ alkyl group, a linear or branched C₂ to C₁₀ alkenyl group, a linear or branched C₂ to C₁₀ alkynyl group, C₃ to C₁₀ cyclic alkyl group, C₃ to C₁₀ hetero-cyclic alkyl group, a C₅ to C₁₀ aryl group, and a C₃ to C₁₀ hetero-aryl group, a C₂ to C₁₀ dialkylamino group, a C₃ to C₁₀ cyclic alkylamino group; wherein R¹ in Formula IA cannot both be methyl, R¹ and R² in Formula IB cannot both be iso-propyl, tert-butyl, and bezenyl and R³ and R⁴ cannot both be methyl and phenyl.

Claims

1. A method for forming a silicon and nitrogen containing film on at least one surface of a substrate by an atomic layer deposition process, the method comprising:

providing the at least one surface of the substrate in a reaction chamber;

introducing at least one aza-polysilane precursor comprising at least two Si—

N bonds, at least one Si—

Si bond, and at least two SiH₂ groups represented by the following Formulae IA, IB, and IC;

2. The method of claim 1 wherein the precursor further comprises a solvent wherein the solvent has a boiling point and wherein the difference between the boiling point of the solvent and that of the at least one aza-polysilane is 40°

C. or less.

3. The method of claim 2 wherein the solvent comprises at least one selected from the group consisting of ether, tertiary amine, alkyl hydrocarbon, aromatic hydrocarbon, tertiary aminoether.

4. The method of claim 1 wherein the at least one aza-polysilane precursor is selected from the group consisting of 3-iso-propyl-3-aza-pentasilane, 3-tert-butyl-3-aza-pentasilane, 3-tert-pentyl-3-aza-pentasilane, 3-cyclopentyl-3-aza-pentasilane, 3-cyclohexyl-3-aza-pentasilane, 3-(2,6-dimethylcyclohexyl-3-aza-pentasilane, 3-(tetrahydropyran-4-yl)-3-aza-pentasilane, 3-(1-methylpiperidin-4-yl)-3-aza-pentasilane, 3-phenyl-3-aza-pentasilane, 3-(2-methyl-tolyl)-3-aza-pentasilane, 3-(2,6-dimethyl-tolyl)-3-aza-pentasilane, 3-(pyridin-3-yl)-3-aza-pentasilane, 3-(4-methylpyridin-3-yl)-3-aza-pentasilane 1,4-bis(cyclopentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(cyclohexyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(2,6-dimethylcyclohexyl)-1,4-Diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(iso-propyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(tert-butyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(tert-pentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane.

5. The method of claim 1 wherein the dialkylaminodisilane comprises di-iso-propylaminodisilane.

6. A method of forming a silicon-containing film via an atomic layer deposition (ALD) process, the method comprising the steps of:

a. providing a substrate in an ALD reactor wherein the substrate is heated to a temperature of less than about 300C;

b. providing in the ALD reactor at least one aza-polysilane precursor represented by the following Formula

7. The method of claim 6 wherein the reacting step is conducted at a temperature of 200°

C. or less.

8. The method of claim 6 wherein the reacting step is conducted at a temperature of 100°

C. or less.

9. The method of claim 6 wherein the reacting step is conducted at 50°

C. or less.

10. The method of claim 6 wherein the method further comprises at least one post-deposition treatment.

11. A method of forming a silicon-containing film onto at least a surface of a substrate using a plasma enhanced atomic layer (PEALD) deposition process, the method comprising:

a. providing a substrate in an ALD reactor;

b. providing in the ALD reactor at least one aza-polysilane precursor comprising at least two Si—

N bonds, at least one Si—

Si bond, and at least two SiH₂ groups represented by the following Formulae;

12. The method of claim 11 wherein the at least one aza-polysilane precursor is selected from the group consisting of 1,4-bis(cyclopentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(cyclohexyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(2,6-dimethylcyclohexyl)-1,4-Diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(iso-propyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(tert-butyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(tert-pentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane.

13. A method of forming a silicon-containing film via an atomic layer deposition (ALD) process, the method comprising the steps of:

a. providing a substrate in an ALD reactor;

b. providing in the ALD reactor at least one aza-polysilane precursor represented by the following Formula IB;

14. The method of claim 13 wherein the at least one aza-polysilane precursor is selected from the group consisting of 1,4-bis(cyclopentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(cyclohexyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(2,6-dimethylcyclohexyl)-1,4-Diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(iso-propyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(tert-butyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, and 1,4-bis(tert-pentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane.

15. The method of claim 13 wherein the ALD process is a plasma enhanced atomic layer (PEALD) process.

16. The method of claim 13 wherein the method further comprises at least one post-deposition treatment.

17. The method of claim 13 wherein the silicon containing film comprises silicon oxide.

18. The method of claim 13 wherein the nitrogen-containing source is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, nitrogen/helium plasma, nitrogen/argon plasma, helium plasma, argon plasma, hydrogen plasma, and mixtures thereof.

19. The method of claim 13 wherein the silicon-containing film is selected from the group consisting of silicon nitride and silicon carbonitride.

20. A method of forming a silicon-containing film via an atomic layer deposition (ALD) process, the method comprising the steps of:

a. providing a substrate in an ALD reactor wherein the substrate is heated to a temperature of less than about 300 C;

b. providing in the ALD reactor at least one aza-polysilane precursor represented by the following Formula

21. A method of forming a silicon-containing film via an atomic layer deposition (ALD) process, the method comprising the steps of:

a. providing a substrate in an ALD reactor;

b. providing in the ALD reactor at least one aza-polysilane precursor represented by the following Formula IB;