METHOD OF DEPOSITING CATALYST ASSISTED SILICATES OF HIGH-K MATERIALS

• US 20080113096A1
• Filed: 11/14/2006
• Published: 05/15/2008
• Est. Priority Date: 11/14/2006
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: MAHAJANI, MAITREYEE
• Granted Patent: US 7,776,395 B2
• Time in Patent Office: Days
• US Class Current: 427/250
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: C23C 16/45534 Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
• CPC Class Codes: C23C 16/45546 specially adapted for a substrate stack in the ALD reactor

Abstract

A high-k silicate atomic layer deposition method is disclosed. To produce a hafnium silicate layer, a substrate may be exposed to a pulse of a hafnium precursor, a pulse of an oxidizer, a pulse of a silicon precursor, and a pulse of another oxidizer. A catalyst may additionally be co-flowed with one or more reactants into the chamber through a separate inlet. Alternatively, the catalyst may be flowed to the chamber before the reactant is introduced in a soaking procedure. By either co-flowing the catalyst through separate inlets or by performing a catalyst soak, hafnium silicate formation may proceed at a fast rate and/or at a low temperature.

Claims

1. A high-k silicate deposition method, sequentially comprising:

(a) positioning at least one substrate in a chamber;

(b) exposing the at least one substrate to a high-k precursor;

(c) exposing the at least one substrate to a first catalyst soak;

(d) exposing the at least one substrate to a first oxidizing source;

(e) exposing the at least one substrate to a silicon precursor;

(f) exposing the at least one substrate to a second catalyst soak; and

then

(g) exposing the at least one substrate to a second oxidizing source.

2. The method of claim 1, wherein the catalyst used in the first and second catalyst soaks are selected from the group consisting of pyridine and ammonia.

3. The method of claim 1, wherein the silicon precursor is selected from the group consisting of hexachlorodisilane and tetrakis-ethoxy-silane.

4. The method of claim 1, further comprising:

exposing the at least one substrate to a purge gas.

5. The method of claim 1, wherein the high-k precursor is a hafnium precursor selected from the group consisting of TDMAH, TEMAH, TDEAH, and HfCl₄.

6. The method of claim 1, further comprising:

repeating (b)-(g) one or more times.

7. The method of claim 1, wherein the first and second oxidizing sources are selected from the group consisting of H₂O, O₃, O₂, or radical oxygen.

8. The method of claim 1, wherein the catalysts used in the first and second catalyst soaks are identical.

9. The method of claim 1, wherein the silicon precursor comprises hexachlorodisilane and the first and second catalyst soaks comprise pyridine as the catalyst.

10. The method of claim 1, wherein the silicon precursor comprises tetrakis-ethoxy-silane and the first and second catalyst soaks comprise ammonia as the catalyst.

11. The method of claim 1, wherein the at least one substrate comprises two or more substrates.

12. The method of claim 1, wherein the at least one substrate comprises about 50 substrates.

13. A high-k silicate deposition method, sequentially comprising:

(a) positioning at least one substrate in a chamber;

(b) exposing the at least one substrate to a high-k precursor;

(c) exposing the at least one substrate to a first oxidizing source and a first catalyst, the first catalyst and the first oxidizing source flowing into the chamber through separate inlets;

(d) exposing the at least one substrate to a silicon precursor; and

then

(e) exposing the at least one substrate to a second oxidizing source and a second catalyst, the second catalyst and the second oxidizing source flowing into the chamber through separate inlets.

14. The method of claim 13, wherein the first and second catalysts are selected from the group consisting of pyridine and ammonia.

15. The method of claim 13, wherein the silicon precursor is selected from the group consisting of hexachlorodisilane and tetrakis-ethoxy-silane.

16. The method of claim 13, further comprising:

exposing the at least one substrate to a purge gas.

17. The method of claim 13, wherein the high-k precursor is a hafnium precursor selected from the group consisting of TDMAH, TEMAH, TDEAH, and HfCl₄.

18. The method of claim 13, further comprising:

repeating (b)-(e) one or more times.

19. The method of claim 13, wherein the first and second oxidizing sources are selected from the group consisting of H₂O, O₃, O₂, or radical oxygen.

20. The method of claim 13, wherein the silicon precursor comprises hexachlorodisilane and the first and second catalysts comprise pyridine.

21. The method of claim 13, wherein the silicon precursor comprises tetrakis-ethoxy-silane and the first and second catalysts comprise ammonia.

22. The method of claim 13, wherein the at least one substrate comprises two or more substrates.

23. The method of claim 13, wherein the at least one substrate comprises about 50 substrates.

24. A hafnium silicate deposition method, sequentially comprising:

positioning at least one substrate in a chamber;

exposing the at least one substrate to a hafnium precursor;

exposing the at least one substrate to water and pyridine, the water and pyridine flowing Into the chamber through separate inlets;

exposing the at least one substrate to hexachlorodisilane; and

then

exposing the at least one substrate to water and pyridine, the water and pyridine flowing into the chamber through separate inlets.

25. The method of claim 24, wherein the at least one substrate comprises two or more substrates.

26. The method of claim 24, wherein the at least one substrate comprises about 50 substrates.