Methods for Depositing Silicon Nitride Films

• US 20150099375A1
• Filed: 09/26/2014
• Published: 04/09/2015
• Est. Priority Date: 10/03/2013
• Status: Active Grant

• Current Assignee: Versum Materials US Inc.
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Mallikarjunan, Anupama, Lei, Xinjian, Kim, Moo-Sung, Cuthill, Kirk Scott, O'Neill, Mark Leonard, Haripin, Chandra
• Granted Patent: US 9,905,415 B2
• Time in Patent Office: Days
• US Class Current: 438/793
• CPC Class Codes: C07F 7/10 containing nitrogen having a Si-N linkage
• CPC Class Codes: C23C 14/027 Graded interfaces
• CPC Class Codes: C23C 14/548 Controlling the composition
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• 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: C23C 16/45542 Plasma being used non-continuously during the ALD reactions
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: C23C 28/42 characterized by the composition of the alternating layers
• 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 21/02222 the compound being a silazane
• 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

Described herein are methods for forming silicon nitride films. In one aspect, there is provided a method of forming a silicon nitride film comprising the steps of: providing a substrate in a reactor; introducing into the reactor an at least one organoaminosilane having a least one SiH₃ group described herein wherein the at least one organoaminosilane reacts on at least a portion of the surface of the substrate to provide a chemisorbed layer; purging the reactor with a purge gas; introducing a plasma comprising nitrogen and an inert gas into the reactor to react with at least a portion of the chemisorbed layer and provide at least one reactive site wherein the plasma is generated at a power density ranging from about 0.01 to about 1.5 W/cm².

Claims

1. A method of forming a silicon nitride film onto at least a surface of a substrate, the method comprising

a. providing a substrate in a reactor;

b. introducing into the reactor an at least one organoaminosilane represented by the following Formulas I, II and III below;

2. The method of claim 1 wherein the at least one organoaminosilane precursor is selected from the group consisting of di-iso-propylaminosilane, di-sec-butylaminosilane, phenylmethylaminosilane, 2,6-dimethylpiperidinosilane, N-methylcyclohexylaminosilane, N-ethylcyclohexylaminosilane, N-isopropylcyclohexylaminosilane, 2-methylpiperidinosilane, N-silyldecahydroquinoline, 2,2,6,6-tetramethylpiperidinosilane, 2-(N-silylmethylamino)pyridine, N-t-butyldisilazane, N-t-pentyldisilazane, N-(3-methyl-2-pyridyl)disilazane, N-(2-methylphenyl)disilazane, N-(2-ethylphenyl)disilazane, N-(2,4,6-trimethylphenyl)disilazane, N-(2,6-di-iso-pripylphenyl)disilazane, di-iso-propylaminodisilane, di-iso-butylaminodisilane, di-sec-butylaminodisilane, 2,6-dimethylpiperidinosilane, N-methylcyclohexylaminodisilane, N-ethylcyclohexylaminodisilane, phenylmethylaminodisilane, 2-(N-disilylmethylamino)pyridine, N-phenylethyldisilane, N-isopropylcyclohexylaminodisilane, 1,1-(N,N′

-di-tert-butylethylenediamino)disilane.

3. The method of claim 1 wherein the plasma comprises a noble gas selected from the group consisting of neon (Ne), argon (Ar), Xenon (Xe), krypton (Kr) and mixtures thereof.

4. The method of claim 1 wherein the silicon nitride film has a density of 2.4 g/cc or greater.

5. The method of claim 1 wherein the method is a vapor deposition process and is selected from the group consisting of at least one selected from plasma enhanced chemical vapor deposition and plasma enhanced cyclic chemical vapor deposition.

6. The method of claim 1 wherein the method is conducted at one or more temperatures of about 400°

C. or less.

7. The method of claim 1 wherein the method is conducted at one or more temperatures of about 300°

C. or less.

8. The method of claim 1 wherein step b further comprises introducing a noble gas into the reactor.

9. A method of forming a silicon nitride film onto at least a surface of a substrate, the method comprising the steps of:

a. providing a substrate in a reactor;

b. introducing into the reactor at least one organoaminosilane precursor is selected from the group consisting of di-iso-propylaminosilane, di-sec-butylaminosilane, phenylmethylaminosilane, 2,6-dimethylpiperidinosilane, N-methylcyclohexylaminosilane, N-ethylcyclohexylaminosilane, N-isopropylcyclohexylaminosilane, 2-methylpiperidinosilane, N-silyldecahydroquinoline, 2,2,6,6-tetramethylpiperidinosilane, 2-(N-silylmethylamino)pyridine, N-t-butyldisilazane, N-t-pentyldisilazane, N-(3-methyl-2-pyridyl)disilazane, N-(2-methylphenyl)disilazane, N-(2-ethylphenyl)disilazane, N-(2,4,6-trimethylphenyl)disilazane, N-(2,6-di-iso-pripylphenyl)disilazane, di-iso-propylaminodisilane, di-iso-butylaminodisilane, di-sec-butylaminodisilane, 2,6-dimethylpiperidinosilane, N-methylcyclohexylaminodisilane, N-ethylcyclohexylaminodisilane, phenylmethylaminodisilane, 2-(N-disilylmethylamino)pyridine, N-phenylethyldisilane, N-isopropylcyclohexylaminodisilane, 1,1-(N,N′

-di-tert-butylethylenediamino)disilane wherein the at least one organoaminosilane reacts on at least a portion of the surface of the substrate to provide a chemisorbed layer;

c. purging the reactor with a purge gas comprising at least one selected from nitrogen, a noble gas, and combinations thereof;

d. introducing a nitrogen-containing plasma into the reactor to react with at least a portion of the chemisorbed layer and provide an at least one reactive site wherein the plasma is generated at a power density ranging from about 0.01 to about 1.5 W/cm²; and

e. optionally purge the reactor with an inert gas; and

wherein the steps b through e are repeated until a desired thickness of the silicon nitride film is obtained.

10. The method of claim 9 wherein the silicon nitride film has a density of 2.4 g/cc or greater.

11. The method of claim 9 wherein method is a vapor deposition process selected from the group consisting of at least one selected from plasma enhanced chemical vapor deposition and plasma enhanced cyclic chemical vapor deposition.

12. The method of claim 9 wherein the method is conducted at a temperature of 400°

C. or less.

13. The method of claim 9 wherein the method is conducted at a temperature of 300°

C. or less.

14. The method of claim 9 where the nitrogen-containing plasma is selected from the group consisting of a nitrogen plasma, an argon/nitrogen plasma, a neon/nitrogen plasma, a krypton/nitrogen plasma, a xenon/nitrogen plasma, and combinations thereof.

15. The method of claim 9 wherein step b further comprises introducing a noble gas into the reactor.

16. The method of claim 9 wherein a plasma comprising hydrogen can be inserted before step d to help remove hydrocarbon generated from the reaction between the organoaminosilane and the surface.

17. The method of claim 16 wherein the plasma comprising hydrogen is selected from the group consisting of hydrogen plasma, hydrogen/helium, hydrogen/argon plasma, hydrogen/neon plasma and mixtures thereof.

18. A method of forming a silicon nitride film onto at least a surface of a substrate, the method comprising the steps of:

a. providing a substrate in a reactor;

b. introducing into the reactor at least one organoaminosilane precursor is selected from the group consisting of di-iso-propylaminosilane, di-sec-butylaminosilane, phenylmethylaminosilane, 2,6-dimethylpiperidinosilane, N-methylcyclohexylaminosilane, N-ethylcyclohexylaminosilane, N-isopropylcyclohexylaminosilane, 2-methylpiperidinosilane, N-silyldecahydroquinoline, 2,2,6,6-tetramethylpiperidinosilane, 2-(N-silylmethylamino)pyridine, N-t-butyldisilazane, N-t-pentyldisilazane, N-(3-methyl-2-pyridyl)disilazane, N-(2-methylphenyl)disilazane, N-(2-ethylphenyl)disilazane, N-(2,4,6-trimethylphenyl)disilazane, N-(2,6-di-iso-pripylphenyl)disilazane, di-iso-propylaminodisilane, di-iso-butylaminodisilane, di-sec-butylaminodisilane, 2,6-dimethylpiperidinosilane, N-methylcyclohexylaminodisilane, N-ethylcyclohexylaminodisilane, phenylmethylaminodisilane, 2-(N-disilylmethylamino)pyridine, N-phenylethyldisilane, N-isopropylcyclohexylaminodisilane, 1,1-(N,N′

-di-tert-butylethylenediamino)disilane wherein the at least one organoaminosilane reacts on at least a portion of the surface of the substrate to provide a chemisorbed layer;

c. purging the reactor with a purge gas comprising at least one selected from nitrogen, a noble gas, and combinations thereof;

d. introducing a plasma comprising a noble gas into the reactor to react with at least a portion of the chemisorbed layer and provide an at least one reactive site wherein the plasma is generated at a power density ranging from about 0.01 to about 1.5 W/cm²; and

e. optionally purge the reactor with an inert gas; and

wherein the steps b through e are repeated until a desired thickness of the silicon nitride film is obtained.

19. The method of claim 18 wherein the silicon nitride film has a density of 2.4 g/cc or greater.

20. The method of claim 18 wherein method is a vapor deposition process selected from the group consisting of at least one selected from plasma enhanced chemical vapor deposition and plasma enhanced cyclic chemical vapor deposition.

21. The method of claim 18 wherein the method is conducted at a temperature of 400°

C. or less.

22. The method of claim 18 wherein the noble gas plasma comprises a noble gas selected from the group consisting of neon (Ne), argon (Ar), Xenon (Xe), krypton (Kr) and mixtures thereof.