Apparatuses and methods for atomic layer deposition of hafnium-containing high-k dielectric materials

• US 20050271813A1
• Filed: 05/12/2005
• Published: 12/08/2005
• Est. Priority Date: 05/12/2004
• Status: Abandoned Application

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Kher, Shreyas, Narwankar, Pravin, Sharangapani, Rahul
• Application Number:
  US11/127,767
• Publication Number:
  US 20050271813A1
• Time in Patent Office: Days
• US Class Current: 427/248.100
• CPC Class Codes: C23C 16/0272 Deposition of sub-layers, e.g. to promote the adhesion of the main coating
• CPC Class Codes: C23C 16/40 Oxides
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/4412 Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps
• CPC Class Codes: C23C 16/4488 by in situ generation of reactive gas by chemical or electrochemical reaction
• CPC Class Codes: C23C 16/45529 specially adapted for making a layer stack of alternating different compositions or gradient compositions
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions
• CPC Class Codes: C23C 16/45544 characterized by the apparatus
• CPC Class Codes: C23C 16/45582 Expansion of gas before it reaches the substrate
• CPC Class Codes: C23C 16/56 After-treatment
• CPC Class Codes: Y02T 50/60 Efficient propulsion technologies, e.g. for aircraft
• CPC Class Codes: Y10T 137/0357 For producing uniform flow
• CPC Class Codes: Y10T 137/0396 Involving pressure control
• CPC Class Codes: Y10T 137/2087 Means to cause rotational flow of fluid [e.g., vortex generator]

Abstract

Embodiments of the invention provide methods for depositing dielectric materials on substrates during vapor deposition processes, such as atomic layer deposition (ALD). In one example, a method includes sequentially exposing a substrate to a hafnium precursor and an oxidizing gas to deposit a hafnium oxide material thereon. In another example, a hafnium silicate material is deposited by sequentially exposing a substrate to the oxidizing gas and a process gas containing a hafnium precursor and a silicon precursor. The oxidizing gas usually contains water vapor formed by flowing a hydrogen source gas and an oxygen source gas through a water vapor generator. In another example, a method includes sequentially exposing a substrate to the oxidizing gas and at least one precursor to deposit hafnium oxide, zirconium oxide, lanthanum oxide, tantalum oxide, titanium oxide, aluminum oxide, silicon oxide, aluminates thereof, silicates thereof, derivatives thereof or combinations thereof.

Claims

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

exposing a substrate to a hafnium precursor to form a hafnium-containing layer thereon;

purging the process chamber with a purge gas;

exposing the substrate to an oxidizing gas to form a hafnium oxide material thereon, wherein the oxidizing gas comprises water vapor formed by flowing a hydrogen source gas and an oxygen source gas through a water vapor generator; and

purging the process chamber with the purge gas.

2. The method of claim 1, wherein the hydrogen source gas comprises hydrogen gas.

3. The method of claim 2, wherein the oxygen source gas comprises an oxygen compound selected from the group consisting of oxygen, nitrous oxide and combinations thereof.

4. The method of claim 3, wherein the oxygen compound flows into the water generator at a faster rate than the hydrogen gas.

5. The method of claim 4, wherein the oxidizing gas further comprises oxygen gas.

6. The method of claim 2, wherein the hydrogen source gas is a forming gas.

7. The method of claim 6, wherein the forming gas has a hydrogen gas concentration in a range from about 1 vol % to about 30 vol %.

8. The method of claim 1, wherein prior to exposing the substrate to the hafnium precursor, the substrate is exposed to a soak process containing the oxidizing gas for a time period in a range from about 5 seconds to about 30 seconds.

9. The method of claim 1, further comprising depositing a silicon oxide material on the hafnium oxide material by:

exposing the substrate to a silicon precursor to form a silicon-containing layer thereon;

purging the process chamber with the purge gas;

exposing the substrate to the oxidizing gas to form the silicon oxide material thereon; and

purging the process chamber with the purge gas.

10. A method for depositing a hafnium-containing material on a substrate during an atomic layer deposition process, comprising:

positioning a substrate within a process chamber;

flowing a hydrogen source gas and an oxygen source gas into a water vapor generator to generate an oxidizing gas comprising water vapor; and

exposing the substrate sequentially to the oxidizing gas and a process gas comprising a hafnium precursor to form a hafnium-containing material on the substrate.

11. The method of claim 10, wherein the hydrogen source gas comprises hydrogen gas.

12. The method of claim 11, wherein the oxygen source gas comprises an oxygen compound selected from the group consisting of oxygen, nitrous oxide and combinations thereof.

13. The method of claim 12, wherein the oxygen compound flows into the water generator at a faster rate than the hydrogen gas.

14. The method of claim 13, wherein the oxidizing gas further comprises oxygen gas.

15. The method of claim 11, wherein the hydrogen source gas is a forming gas.

16. The method of claim 15, wherein the forming gas has a hydrogen gas concentration in a range from about 1 vol % to about 30 vol %.

17. The method of claim 10, wherein the hafnium-containing material is selected from the group consisting of hafnium oxide, hafnium silicate, hafnium silicon oxynitride, hafnium oxynitride, hafnium aluminate, derivatives thereof and combinations thereof.

18. The method of claim 17, wherein the process gas further comprises a silicon precursor or an aluminum precursor.

19. The method of claim 10, wherein prior to forming the hafnium-containing material, the substrate is exposed to a soak process containing the oxidizing gas for a time period in a range from about 5 seconds to about 30 seconds.

20. A method for forming a dielectric material on a substrate during an atomic layer deposition process, comprising:

positioning a substrate within a process chamber;

flowing a hydrogen source gas and an oxygen source gas into a water vapor generator to form an oxidizing gas comprising a water vapor; and

exposing the substrate sequentially to the oxidizing gas and at least one precursor to form a dielectric material thereon.

21. The method of claim 20, wherein the at least one precursor is selected from the group consisting of a hafnium precursor, a zirconium precursor, a silicon precursor, an aluminum precursor, a tantalum precursor, a titanium precursor, a lanthanum precursor and combinations thereof.

22. The method of claim 21, wherein the dielectric material comprises at least one material selected from the group consisting of hafnium oxide, hafnium silicate, zirconium oxide, zirconium silicate, lanthanum oxide, lanthanum silicate, tantalum oxide, tantalum silicate, titanium oxide, titanium silicate, aluminum oxide, aluminum silicate, silicon oxide, derivatives thereof and combinations thereof.

23. The method of claim 20, wherein prior to forming the dielectric material, the substrate is exposed to a soak process containing the oxidizing gas for a time period in a range from about 5 seconds to about 30 seconds.

24. A method for depositing a hafnium silicate material on a substrate during an atomic layer deposition process, comprising:

positioning a substrate within a process chamber;

flowing a hydrogen source gas and an oxygen source gas into a water vapor generator to form an oxidizing gas comprising a water vapor; and

exposing the substrate sequentially to the oxidizing gas and a process gas comprising a hafnium precursor and a silicon precursor to form a hafnium silicate material thereon.

25. The method of claim 24, wherein the process gas is formed by combining within the process chamber a first gas containing the hafnium precursor and a second gas containing the silicon precursor.

26. The method of claim 24, wherein the process gas is formed by vaporizing a reagent mixture containing the hafnium precursor and the silicon precursor.

27. A method for forming a hafnium-containing dielectric stack on a substrate within a process chamber, comprising:

flowing a hydrogen source gas and an oxygen source gas into a water vapor generator to form an oxidizing gas comprising water vapor; and

forming at least one hafnium oxide layer and at least one hafnium silicate layer on a substrate comprising;

exposing the substrate sequentially to the oxidizing gas and a first process gas comprising a hafnium precursor to form a first hafnium-containing material thereon; and

exposing the substrate sequentially to the oxidizing gas and a second process gas comprising the hafnium precursor to form a second hafnium-containing material on the first hafnium-containing material.

28. The method of claim 27, wherein the first process gas further comprises a silicon precursor.

29. The method of claim 27, wherein the second process gas further comprises a silicon precursor.

30. The method of claim 28, wherein prior to forming the first hafnium-containing material, the substrate is exposed to a soak process containing the oxidizing gas for a time period in a range from about 5 seconds to about 30 seconds.