Pretreatment processes within a batch ALD reactor

• US 20070049053A1
• Filed: 08/26/2005
• Published: 03/01/2007
• Est. Priority Date: 08/26/2005
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Mahajani, Maitreyee
• Granted Patent: US 7,402,534 B2
• Time in Patent Office: Days
• US Class Current: 438/785
• CPC Class Codes: C23C 16/0218 in a reactive atmosphere C23C16/0227 takes precedence
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions
• CPC Class Codes: C23C 16/45546 specially adapted for a substrate stack in the ALD reactor
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/3141 Deposition using atomic layer deposition techniques [ALD]
• CPC Class Codes: H01L 21/3142 of nano-laminates, e.g. alternating layers of Al203-Hf02

Abstract

Embodiments of the invention provide methods for forming a material on a substrate which includes exposing a plurality of substrates within a batch process chamber to a first oxidizing gas during a pretreatment process, exposing the substrates sequentially to a precursor and a second oxidizing gas during an ALD cycle and repeating the ALD cycle to form a material on the substrates. In a preferred example, a hafnium precursor is used during the ALD process to form a hafnium-containing material, such as hafnium oxide. In one example, the first and second oxidizing gases are the same oxidizing gases. In a preferred example, the first and second oxidizing gases are different oxidizing gases, such that the pretreatment process contains ozone and the ALD process contains water vapor.

Claims

1. A method for forming a hafnium material on a substrate within a process chamber, comprising:

exposing a plurality of substrates within a batch process chamber to a first oxidizing gas during a pretreatment process;

exposing the plurality of substrates sequentially to a second oxidizing gas and a process gas containing a hafnium precursor during an ALD cycle, wherein the first and second oxidizing gases are different oxidizing gases; and

repeating the ALD cycle to form a hafnium-containing layer having a predetermined thickness.

2. The method of claim 1, wherein the hafnium-containing layer comprises hafnium oxide.

3. The method of claim 1, wherein the first oxidizing gas and the second oxidizing gas are each independently selected from that group consisting of oxygen, ozone, atomic-oxygen, water, hydrogen peroxide, nitrous oxide, nitric oxide, derivatives thereof and combinations thereof.

4. The method of claim 3, wherein the first oxidizing gas contains ozone and the second oxidizing gas contains water.

5. The method of claim 3, wherein the first oxidizing gas contains water and the second oxidizing gas contains ozone.

6. The method of claim 3, wherein the pretreatment process occurs for a time period within a range from about 1 second to about 5 minutes.

7. The method of claim 3, wherein the pretreatment process occurs for a time period within a range from about 5 minutes to about 60 minutes.

8. The method of claim 7, wherein the plurality of substrates contains at least 25 substrates.

9. The method of claim 8, wherein the plurality of substrates contains about 50 substrates or more.

10. The method of claim 9, wherein the plurality of substrates contains about 100 substrates.

11. The method of claim 1, wherein the process gas further comprises a silicon precursor.

12. The method of claim 11, wherein the hafnium-containing layer comprises hafnium silicate.

13. A method for forming a hafnium material on a substrate within a process chamber, comprising:

exposing a plurality of substrates within a batch process chamber to a first oxidizing gas for a predetermined time during a pretreatment process;

conducting an ALD cycle, comprising;

the plurality of substrates to a hafnium precursor for a time period of at least about 30 seconds;

the batch process chamber to a first purge process;

the plurality of substrates to a second oxidizing gas for a time period of at least about 30 seconds; and

exposing the batch process chamber to a second purge process; and

repeating the ALD cycle to form a hafnium-containing layer having a predetermined thickness.

14. The method of claim 13, wherein predetermined time of the pretreatment process last for a time period within a range from about 1 second to about 5 minutes.

15. The method of claim 13, wherein predetermined time of the pretreatment process last for a time period within a range from about 5 minutes to about 60 minutes.

16. The method of claim 13, wherein the first oxidizing gas and the second oxidizing gas are each independently selected from that group consisting of oxygen, ozone, atomic-oxygen, water, hydrogen peroxide, nitrous oxide, nitric oxide, derivatives thereof and combinations thereof.

17. The method of claim 16, wherein the first oxidizing gas contains ozone and the second oxidizing gas contains water.

18. The method of claim 16, wherein the first oxidizing gas contains water and the second oxidizing gas contains ozone.

19. The method of claim 13, wherein the hafnium precursor is exposed to the plurality of substrates for a time period within a range from about 30 seconds to about 90 seconds.

20. The method of claim 19, wherein the second oxidizing gas is exposed to the plurality of substrates for a time period within a range from about 30 seconds to about 90 seconds.

21. The method of claim 16, wherein the plurality of substrates contains at least 25 substrates or more.

22. The method of claim 21, wherein the first oxidizing gas and the second oxidizing gas are different oxidizing gases.

23. The method of claim 21, wherein the first oxidizing gas and the second oxidizing gas are the same oxidizing gases.

24. The method of claim 13, wherein the ALD cycle further comprises sequentially exposing the plurality of substrates to a silicon precursor and the second oxidizing gas.

25. The method of claim 24, wherein the hafnium-containing layer comprises hafnium silicate.

26. A method for forming a hafnium material on a substrate within a process chamber, comprising:

exposing a plurality of substrates within a batch process chamber to a pretreatment process;

exposing the plurality of substrates sequentially to a hafnium precursor and a precursor gas during an ALD cycle; and

repeating the ALD cycle to form a hafnium-containing layer having a predetermined thickness.

27. The method of claim 26, wherein the pretreatment process occurs for a time period within a range from about 1 second to about 5 minutes.

28. The method of claim 26, wherein the pretreatment process occurs for a time period within a range from about 5 minutes to about 60 minutes.

29. The method of claim 28, wherein the pretreatment process contains a first oxidizing gas.

30. The method of claim 29, wherein the precursor gas comprises a second oxidizing gas.

31. The method of claim 30, wherein the first oxidizing gas and the second oxidizing gas are each independently selected from that group consisting of oxygen, ozone, atomic-oxygen, water, hydrogen peroxide, nitrous oxide, nitric oxide, derivatives thereof and combinations thereof.

32. The method of claim 26, wherein the plurality of substrates contains at least 25 substrates or more.