Compositions and methods for the deposition of silicon oxide films

• US 10,703,915 B2
• Filed: 09/08/2017
• Issued: 07/07/2020
• Est. Priority Date: 09/19/2016
• Status: Active Grant

• Current Assignee: Versum Materials US, LLC (Merck & Co., Inc.)
• Original Assignee: Versum Materials US, LLC (Merck & Co., Inc.)
• Inventors: Lei, Xinjian, Wang, Meiliang, MacDonald, Matthew R., Ho, Richard, Xiao, Manchao, Rajaraman, Suresh Kalpatu
• Primary Examiner(s): Burkhart, Elizabeth A
• Application Number:
  US15/698,794
• Publication Number:
  US 20180127592A1
• Time in Patent Office: 1,033 Days
• Field of Search: 427569-579
• CPC Class Codes: C01B 33/126 Preparation of silica of undetermined type
• CPC Class Codes: C01P 2002/54 one element only
• CPC Class Codes: C01P 2006/10 Solid density
• 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: C09D 1/00 Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/402 Silicon dioxide
• CPC Class Codes: C23C 16/45527 characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
• CPC Class Codes: C23C 16/45536 Use of plasma, radiation or electromagnetic fields
• 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

Abstract

Described herein are compositions and methods for forming silicon oxide films. In one aspect, the film is deposited from at least one silicon precursor compound, wherein the at least one silicon precursor compound is selected from the following Formulae A and B:

as defined herein.

Claims

1. A method of depositing a film comprising silicon and oxygen onto a substrate, the method comprising the steps of:

a) providing a substrate in a reactor;

b) introducing into the reactor at least one silicon precursor compound, wherein the at least one silicon precursor compound is selected from the group consisting of Formulae A and B;

2. The method of claim 1, wherein the at least one silicon precursor compound is at least one selected from the group consisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1-diethylamino-1,1,3,3,3-pentamethyldisiloxane, 1-di-iso-propylamino-1,1,3,3,3-pentamethyldisiloxane, 1-di-sec-butylamino-1,1,3,3,3-pentamethyldisiloxane, 1-pyrrolyl-1,1,3,3,3-pentamethyldisiloxane, 1-pyrrolidino-1,1,3,3,3-pentamethyldisiloxane, 1-piperidino-1,1,3,3,3-pentamethyldisiloxane, 1-(2,6-dimethylpiperidino)-3,3,3-pentamethyldisiloxane, 1-dimethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-diethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-di-iso-propylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-sec-butylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-cyclohexylmethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-cyclohexylethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-piperidino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-(2,6-dimethylpiperidino)-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-pyrrolyl-1,1,3,3,5,5,5-heptamethyltrisiloxane, and 1-pyrrolidino-1,1,3,3,5,5,5-heptamethyltrisiloxane.

3. The method of claim 1, wherein the oxygen-containing source is selected from the group consisting of an oxygen plasma, a plasma comprising oxygen and argon, a plasma comprising oxygen and helium, an ozone plasma, a water plasma, a nitrous oxide plasma, a carbon dioxide plasma, a carbon monoxide plasma, and combinations thereof.

4. The method of claim 1 wherein the oxygen-containing source comprises plasma.

5. The method of claim 4 wherein the plasma is generated in situ.

6. The method of claim 4 wherein the plasma is generated remotely.

7. The method of claim 4 wherein the film has a density of about 2.1 g/cc or greater.

8. The method of claim 1 wherein the film further comprises carbon.

9. The method of claim 8 wherein the film has a density of about 1.8 g/cc or greater.

10. The method of claim 8 wherein a carbon content of the film is 0.5 atomic weight percent (at. %) as measured by x-ray photospectroscopy or greater.

11. The method of claim 1 wherein the at least one silicon precursor compound is selected from the group consisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1-diethylamino-1,1,3,3,3-pentamethyldisiloxane, and 1-pyrrolidino-1,1,3,3,3-pentamethyldisiloxane.

12. The method of claim 11 wherein the at least one silicon precursor compound is 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane.

13. The method of claim 1 wherein the at least one silicon precursor compound is substantially free of halide ions.

14. The method of claim 13 wherein the at least one silicon precursor compound comprises less than 5 ppm of halide ions.

15. The method of claim 14 wherein the at least one silicon precursor compound comprises less than 3 ppm of halide ions.

16. The method of claim 15 wherein the at least one silicon precursor compound comprises less than 1 ppm of halide ions.

17. The method of claim 16 wherein the at least one silicon precursor compound is free of halide ions.

18. A method of depositing a film comprising silicon and oxygen onto a substrate comprises steps of:

a) providing a substrate in a reactor;

b) introducing into the reactor at least one silicon precursor compound, wherein the at least one silicon precursor compound is selected from the group consisting of Formulae A and B;

19. The method of claim 18, wherein the at least one silicon precursor compound is at least one selected from the group consisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1-diethylamino-1,1,3,3,3-pentamethyldisiloxane, 1-di-iso-propylamino-1,1,3,3,3-pentamethyldisiloxane, 1-di-sec-butylamino-1,1,3,3,3-pentamethyldisiloxane, 1-pyrrolyl-1,1,3,3,3-pentamethyldisiloxane, 1-pyrrolidino-1,1,3,3,3-pentamethyldisiloxane, 1-piperidino-1,1,3,3,3-pentamethyldisiloxane, 1-(2,6-dimethylpiperidino)-3,3,3-pentamethyldisiloxane, 1-dimethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-diethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-di-iso-propylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-sec-butylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-cyclohexylmethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-cyclohexylethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-piperidino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-(2,6-dimethylpiperidino)-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-pyrrolyl-1,1,3,3,5,5,5-heptamethyltrisiloxane, and 1-pyrrolidino-1,1,3,3,5,5,5-heptamethyltrisiloxane.

20. The method of claim 18, wherein the at least one silicon precursor compound is at least one selected from the group consisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1-diethylamino-1,1,3,3,3-pentamethyldisiloxane, and 1-pyrrolidino-1,1,3,3,3-pentamethyldisiloxane.

21. The method of claim 20 wherein the at least one silicon precursor compound is 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane.

22. The method of claim 18 wherein the at least one silicon precursor compound is substantially free of halide ions.

23. The method of claim 22 wherein the at least one silicon precursor compound comprises less than 5 ppm of halide ions.

24. The method of claim 23 wherein the at least one silicon precursor compound comprises less than 3 ppm of halide ions.

25. The method of claim 24 wherein the at least one silicon precursor compound comprises less than 1 ppm of halide ions.

26. The method of claim 25 wherein the at least one silicon precursor compound is free of halide ions.