Methods for depositing silicon nitride films

• US 9,905,415 B2
• Filed: 09/26/2014
• Issued: 02/27/2018
• Est. Priority Date: 10/03/2013
• Status: Active Grant

• Current Assignee: Versum Materials US, LLC (Merck & Co., Inc.)
• Original Assignee: Versum Materials US, LLC (Merck & Co., Inc.)
• Inventors: Chandra, Haripin, Mallikarjunan, Anupama, Lei, Xinjian, Kim, Moo-Sung, Cuthill, Kirk Scott, O'Neill, Mark Leonard
• Primary Examiner(s): Chen, Bret P
• Application Number:
  US14/498,044
• Publication Number:
  US 20150099375A1
• Time in Patent Office: 1,250 Days
• 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

Methods for forming silicon nitride films are disclosed that comprise 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 plasma enhanced atomic layer deposition 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 method is conducted at one or more temperatures of about 400°

C. or less.

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

C. or less.

6. A plasma enhanced atomic layer deposition 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 said introducing is for a period of 0.2 to 5 seconds and the at least one organoaminosilane reacts on at least a portion of the surface of the substrate;

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-noble gas containing plasma into the reactor; and

e. 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 wherein the nitride film has a refractive index of greater than 1.9 and a density of greater than 2.7 g/cc.

7. The method of claim 6 wherein the method is conducted at a temperature of 400°

C. or less.

8. The method of claim 6 wherein the method is conducted at a temperature of 300°

C. or less.

9. The method of claim 6 where the nitrogen-noble gas containing plasma consists essentially of a member selected from the group consisting of an argon/nitrogen plasma, a neon/nitrogen plasma, a krypton/nitrogen plasma, a xenon/nitrogen plasma, and combinations thereof.

10. A plasma enhanced atomic layer deposition 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. 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;

wherein the silicon nitride film has a density of at least 2.7 g/cc.

11. The method of claim 10 wherein the method is conducted at a temperature of 400°

C. or less.

12. The method of claim 10 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.

13. A plasma enhanced atomic layer deposition 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 Formula below;

14. The method of claim 13 wherein the organoaminosilane comprises at least one member selected from the group consisting of 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, and 1,1-(N,N′

-di-tert-butylethylenediamino)disilane; and

the plasma further consists essentially of a argon.

15. A plasma enhanced atomic layer deposition 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 for a period of about 0.001 to about 500 seconds at least one organoaminosilane represented by the following Formula I below;