PRETREATMENT PROCESSES WITHIN A BATCH ALD REACTOR

• US 20080261413A1
• Filed: 06/27/2008
• Published: 10/23/2008
• 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 7,972,978 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 21/02148 the material containing hafnium, e.g. HfSiOx or HfSiON
• 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 hafnium material on a substrate within a processing chamber. In one embodiment, a method is provided which includes exposing the substrate within the processing chamber to a first oxidizing gas during a pretreatment process, exposing the substrate sequentially to a second oxidizing gas and a deposition gas during an atomic layer deposition (ALD) cycle, wherein the second oxidizing gas contains water and the deposition gas contains a hafnium amino compound, and repeating the ALD cycle to form a hafnium-containing layer having a thickness within a range from about 5 Å to about 300 Å. In one example, the first oxidizing gas contains an O₃/O₂ mixture having an ozone concentration within a range from about 5 atomic percent to about 30 atomic percent.

Claims

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

exposing a substrate within a processing chamber to a first oxidizing gas during a pretreatment process, wherein the first oxidizing gas comprises an O₃/O₂ mixture having an ozone concentration within a range from about 5 atomic percent to about 30 atomic percent;

exposing the substrate sequentially to a second oxidizing gas and a deposition gas during an atomic layer deposition cycle, wherein the second oxidizing gas comprises water and the deposition gas comprises a hafnium amino compound; and

repeating the atomic layer deposition cycle to form a hafnium-containing layer having a thickness within a range from about 5 Å

to about 300 Å

.

2. The method of claim 1, wherein the hafnium-containing layer comprises hafnium oxide having the chemical formula of HfO_x, whereas x is about 1.8.

3. The method of claim 1, wherein the deposition gas further comprises a silicon precursor.

4. The method of claim 3, wherein the hafnium-containing layer comprises hafnium silicate.

5. The method of claim 3, wherein the silicon precursor comprises silane, disilane, or derivatives thereof.

6. The method of claim 3, wherein the silicon precursor comprises an alkylamino silane.

7. The method of claim 6, wherein the alkylamino silane is selected from the group consisting of tetrakis(dimethylamino) silane, tetrakis(diethylamino) silane, tris(dimethylamino) silane, tris(diethylamino) silane, and derivatives thereof.

8. The method of claim 1, wherein the hafnium amino compound is tetrakis(diethylamino) hafnium, tetrakis(dimethylamino) hafnium, or tetrakis(ethylmethylamino) hafnium.

9. The method of claim 8, wherein the ozone concentration is within a range from about 10 atomic percent to about 20 atomic percent.

10. The method of claim 8, wherein the thickness of the hafnium-containing layer is within a range from about 20 Å

to about 100 Å

.

11. A method for forming a hafnium material on a substrate within a processing chamber, comprising:

exposing a substrate within a processing chamber to a first oxidizing gas during a pretreatment process, wherein the first oxidizing gas comprises an O₃/O₂ mixture having an ozone concentration within a range from about 1 atomic percent to about 50 atomic percent;

conducting an atomic layer deposition cycle, comprising;

exposing the substrate to a hafnium precursor gas comprising a hafnium amino compound for a time period of at least about 30 seconds;

purging the processing chamber;

exposing the substrate to a second oxidizing gas comprising water for a time period of at least about 30 seconds; and

purging the processing chamber; and

repeating the atomic layer deposition cycle to form a hafnium-containing layer.

12. The method of claim 11, wherein the ozone concentration is within a range from about 5 atomic percent to about 30 atomic percent.

13. The method of claim 12, wherein the ozone concentration is within a range from about 10 atomic percent to about 20 atomic percent.

14. The method of claim 11, wherein the hafnium-containing layer is deposited having a thickness within a range from about 5 Å

to about 300 Å

.

15. The method of claim 14, wherein the thickness is within a range from about 20 Å

to about 100 Å

.

16. The method of claim 11, wherein the substrate is exposed to the hafnium precursor gas for a time period within a range from about 30 seconds to about 90 seconds.

17. The method of claim 11, wherein the substrate is exposed to the second oxidizing gas for a time period within a range from about 30 seconds to about 90 seconds.

18. The method of claim 11, wherein the atomic layer deposition cycle further comprises sequentially exposing the substrate to a silicon precursor and the second oxidizing gas, and the hafnium-containing layer comprises hafnium silicate.

19. The method of claim 11, wherein the hafnium amino compound is tetrakis(diethylamino) hafnium, tetrakis(dimethylamino) hafnium, or tetrakis(ethylmethylamino) hafnium.

20. A method for forming a hafnium material on a substrate within a processing chamber, comprising:

exposing a substrate to water within a processing chamber during a pretreatment process;

exposing the substrate sequentially to a hafnium precursor gas and an oxidizing precursor gas during an atomic layer deposition cycle, wherein the hafnium precursor gas comprises a hafnium amino compound, the oxidizing precursor gas comprises an O₃/O₂ mixture having an ozone concentration within a range from about 1 atomic percent to about 50 atomic percent, and the substrate is heated to a temperature within a range from about 200°

C. to about 400°

C. during the atomic layer deposition cycle; and

repeating the atomic layer deposition cycle to form a hafnium-containing layer.

21. The method of claim 20, wherein the pretreatment process occurs for a time period within a range from about 1 second to about 5 minutes.

22. The method of claim 20, wherein the hafnium-containing layer is deposited having a thickness within a range from about 5 Å

to about 300 Å

.

23. The method of claim 22, wherein the thickness is within a range from about 20 Å

to about 100 Å

.

24. The method of claim 20, wherein the ozone concentration is within a range from about 5 atomic percent to about 30 atomic percent.

25. The method of claim 24, wherein the ozone concentration is within a range from about 10 atomic percent to about 20 atomic percent.