Formation of a silicon oxynitride layer on a high-k dielectric material

• US 8,119,210 B2
• Filed: 05/21/2004
• Issued: 02/21/2012
• Est. Priority Date: 05/21/2004
• Status: Expired due to Fees

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Narwankar, Pravin K., Higashi, Gregg
• Primary Examiner(s): Gambetta, Kelly M
• Application Number:
  US10/851,561
• Publication Number:
  US 20050260347A1
• Time in Patent Office: 2,832 Days
• Field of Search: 427/569
• US Class Current: 427/569
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: H01L 21/0214 the material being a silicon oxynitride, e.g. SiON or SiON:H
• CPC Class Codes: H01L 21/02148 the material containing hafnium, e.g. HfSiOx or HfSiON
• CPC Class Codes: H01L 21/02178 the material containing aluminium, e.g. Al2O3
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02192 the material containing at least one rare earth metal element, e.g. oxides of lanthanides, scandium or yttrium
• CPC Class Codes: H01L 21/02211 the compound being a silane, e.g. disilane, methylsilane or chlorosilane
• CPC Class Codes: H01L 21/02219 the compound comprising silicon and nitrogen
• CPC Class Codes: H01L 21/02271 deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition H01L21/02266 takes precedence
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/02332 into an oxide layer, e.g. changing SiO to SiON
• CPC Class Codes: H01L 21/0234 treatment by exposure to a plasma
• CPC Class Codes: H01L 21/02362 formation of intermediate layers, e.g. capping layers or diffusion barriers
• CPC Class Codes: H01L 21/3141 Deposition using atomic layer deposition techniques [ALD]
• CPC Class Codes: H01L 21/3143 composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers

Abstract

In one embodiment, a method for depositing a capping layer on a dielectric layer in a process chamber is provided which includes depositing the dielectric layer on a substrate surface, depositing a silicon-containing layer by an ALD process, comprising alternately pulsing a silicon precursor and an oxidizing gas into the process chamber, and exposing the silicon-containing layer to a nitridation process. In another embodiment, a method for depositing a silicon-containing capping layer on a dielectric layer in a process chamber by an ALD process is provided which includes flowing a silicon precursor into the process chamber, purging the process chamber with a purge gas, flowing an oxidizing gas comprising water formed by flowing a H₂ gas and an oxygen-containing gas through a water vapor generator, and purging the process chamber with the purge gas.

Claims

1. A method for depositing a capping layer on a dielectric layer, comprising:

depositing the dielectric layer on a substrate by a first ALD process from a first group of gases, depositing the dielectric layer composing alternately pulsing a high-k precursor and a water formed oxidizing gas to the substrate surface, wherein the dielectric layer is a high-k layer;

depositing a silicon-containing layer on the dielectric layer by an second ALD process from a second group of gases, depositing the silicon-containing layer comprising alternately pulsing a silicon precursor and an oxidizing gas into a process chamber, wherein the oxidizing gas comprises water formed by flowing a hydrogen-containing gas and an oxygen-containing gas through a catalytic water vapor generator;

exposing the silicon-containing layer to a nitridation process; and

exposing the substrate to a anneal process.

2. The method of claim 1, wherein the nitridation process comprises a nitrogen plasma.

3. The method of claim 2, wherein the anneal process is at a temperature within a range from about 600°

C. to about 1,200°

C. for a time period within a range from about 1 second to about 120 seconds.

4. The method of claim 3, wherein the silicon-containing layer is about 5 Å

or less.

5. The method of claim 1, wherein the dielectric layer comprises a material selected from the group consisting of hafnium oxide, hafnium silicate, hafnium silicon oxynitride, hafnium aluminum oxynitride, aluminum oxide, laminate of hafnium oxide and aluminum oxide, lanthanum aluminum oxide, lanthanum oxide, derivatives thereof, and combinations thereof.

6. The method of claim 5, wherein the depositing the dielectric layer, the depositing the silicon-containing layer, and the nitridation process occur in the same process chamber.

7. The method of claim 5, wherein the catalytic water vapor generator comprises a catalyst-lined reactor or a catalyst cartridge.

8. The method of claim 7, wherein the oxygen-containing gas comprises at least one gas selected from the group consisting of O₂, N₂O, NO₂, N₂O₅ and combinations thereof.

9. The method of claim 8, wherein the silicon precursor is selected from the group consisting of (Me₂N)₄Si, (Me₂N)₃SiH, (Et₂N)₄Si, (Et₂N)₃SiH, (MeEtN)₄Si, (MeEtN)₃SiH, SiH₄, SiCl₄, H₂SiCl₂, Si₂H₆, Si₂Cl₆, derivatives thereof, and combinations thereof.

36. The method of claim 1, wherein the catalytic water vapor generator comprises a catalyst material selected from the group consisting of palladium, platinum, nickel alloys thereof, and combinations thereof.

37. The method of claim 36, wherein the oxidizing gas comprises an oxygen enriched water vapor.

38. The method of claim 36, wherein the oxidizing gas comprises a hydrogen enriched water vapor.

10. A method for depositing a capping layer on a dielectric layer in a process chamber, comprising:

depositing the dielectric layer on a substrate by a first ALD process, wherein the dielectric layer is a high-k layer formed by alternately pulsing a high-k precursor and a water formed oxidizing gas to the substrate surface through a catalytic water vapor generator;

exposing the dielectric layer to a second ALD process from a second group of gases, comprising alternately pulsing a silicon precursor and an oxidizing gas into the process chamber, wherein the oxidizing gas comprises water formed by flowing a hydrogen-containing gas and an oxygen-containing gas through the catalytic water vapor generator, the second ALD process depositing a silicon-containing layer on the dielectric layer; and

exposing the silicon-containing layer to a nitridation process.

11. The method of claim 10, wherein the catalytic water vapor generator comprises a catalyst-lined reactor or a catalyst cartridge.

12. The method of claim 11, wherein the oxygen-containing gas comprises at least one gas selected from the group consisting of O₂, N₂O, NO₂, N₂O₅ and combinations thereof.

13. The method of claim 12, wherein the silicon precursor is selected from the group consisting of (Me₂N)₄Si, (Me₂N)₃SiH, (Et₂N)₄Si, (Et₂N)₃SiH, (MeEtN)₄Si, (MeEtN)₃SiH, SiH₄, SiCl₄, H₂SiCl₂, Si₂H₆, Si₂Cl₆, derivatives thereof and combinations thereof.

14. The method of claim 10, wherein the nitridation process comprises a nitrogen plasma.

15. The method of claim 14, wherein the substrate is annealed for a time period within a range from about 1 second to about 120 seconds and at a temperature from about 600°

C. to about 1,200°

C.

16. The method of claim 14, wherein a polysilicon layer is deposited to the capping layer.

17. The method of claim 15, wherein the silicon-containing layer is about 5 Å

or less.

18. The method of claim 17, wherein the dielectric layer is selected from the group consisting of hafnium oxide, hafnium silicate, hafnium silicon oxynitride, hafnium aluminum oxynitride, aluminum oxide, laminate of hafnium oxide and aluminum oxide, lanthanum aluminum oxide, lanthanum oxide, derivatives thereof, and combinations thereof.

19. The method of claim 10, wherein the depositing the dielectric layer, the depositing the silicon-containing layer and the nitridation process occur in the processing chamber.

39. The method of claim 10, wherein the catalytic water vapor generator comprises a catalyst material selected from the group consisting of palladium, platinum, nickel, alloys thereof, and combinations thereof.

40. The method of claim 39, wherein the oxidizing gas comprises an oxygen enriched water vapor.

41. The method of claim 39, wherein the oxidizing gas comprises a hydrogen enriched water vapor.

20. A method for depositing a silicon-containing capping layer on a dielectric layer in a process chamber by an ALD process, comprising:

providing a substrate having a dielectric layer disposed thereon into an ALD process chamber, wherein the dielectric layer is a hafnium oxide containing layer formed from a first ALD process from a first group of gases by alternation pulsing a hafnium containing precursor and water formed oxidizing gas; and

performing a second ALD process comprising;

flowing a second group of gases comprising a silicon precursor into the ALD process chamber;

purging the process chamber with a purge gas;

flowing an oxidizing gas into the process chamber to form a silicon-containing capping layer, the oxidizing gas comprising hydrogen enriched water formed by flowing a hydrogen-containing gas and a oxygen-containing gas through a catalytic water vapor generator; and

purging the process chamber with the purge gas.

21. The method of claim 20, wherein the oxygen-containing gas comprises at least one gas selected from the group consisting of O₂, N₂O, NO₂, N₂O₅ and combinations thereof.

22. The method of claim 21, wherein the silicon-containing capping layer is exposed to a plasma nitridation process.

23. The method of claim 22, wherein the silicon-containing capping layer is annealed at a temperature from about 600°

C. to about 1,200°

C. for a time period within a range form about 1 second to about 120 seconds.

24. The method of claim 21, wherein the silicon precursor is selected from the group consisting of (Me₂N)₄Si, (Me₂N)₃SiH, (Et₂N)₄Si, (Et₂N)₃SiH, (MeEtN)₄Si, (MeEtN)₃SiH, SiH₄, SiCl₄, H₂SiCl₂, Si₂H₆, Si₂Cl₆, derivatives thereof and combinations thereof.

25. The method of claim 24, wherein a polysilicon layer is deposited to the silicon-containing capping layer.

26. The method of claim 24, wherein the silicon-containing capping layer is about 5 Å

or less.

27. The method of claim 26, wherein the dielectric layer comprises a material selected from the group consisting of hafnium oxide, hafnium silicate, hafnium silicon oxynitride, hafnium aluminum oxynitride, aluminum oxide, laminate of hafnium oxide and aluminum oxide, lanthanum aluminum oxide, lanthanum oxide, derivatives thereof, and combinations thereof.

42. The method of claim 20, wherein the catalytic water vapor generator comprises a catalyst material selected from the group consisting of palladium, platinum, nickel alloys thereof, and combinations thereof.

28. A method for depositing a silicon-containing layer on a substrate surface in a process chamber, comprising:

exposing the substrate having a hafnium containing dielectric layer formed from a first ALD process from a first gas mixture by alternately pulsing a hafnium containing precursor and water formed oxidizing gas to a second gas mixture comprising a silicon precursor and an oxidizing gas during a second ALD process to form a silicon oxide layer on the hafnium containing dielectric layer, wherein the oxygen-containing gas through a water vapor generator; and

exposing the silicon oxide layer to a nitridation process.

29. The method of claim 28, wherein the oxygen-containing gas comprises at least one gas selected from the group consisting of O₂, N₂O, NO₂, N₂O₅ and combinations thereof.

30. The method of claim 29, wherein the nitridation process comprises a nitrogen plasma.

31. The method of claim 30, wherein the silicon-containing layer is annealed at a temperature from about 600°

C. to about 1,200°

C. for a time period from about 1 second to about 120 seconds.

32. The method of claim 30, wherein the silicon precursor is selected from the group consisting of (Me₂N)₄Si;

(Me₂N)₃SiH, (Et₂N)₄Si, (Et₂N)₃SiH, (MeEtN)₄Si, (MeEtN)₃SiH, SiH₄, SiCl₄, H₂SiCl₂, Si₂H₆, Si₂Cl₆, derivatives thereof and combinations thereof.

33. The method of claim 32, wherein a polysilicon layer is deposited on the silicon layer.

34. The method of claim 32, wherein the silicon oxide layer has a thickness of about 5 Å

or less.

35. The method of claim 34, wherein the dielectric layer comprises a material selected from the group consisting of hafnium oxide, hafnium silicate, hafnium silicon oxynitride, hafnium aluminum oxynitride, laminate of hafnium oxide and aluminum oxide, lanthanum aluminum oxide, lanthanum oxide, aluminum oxide, derivatives thereof, and combinations.

43. The method of claim 28, wherein the catalytic water vapor generator comprises a catalyst material selected from the group consisting of palladium, platinum, nickel alloys thereof, and combinations thereof.

44. The method of claim 43, wherein the oxidizing gas comprises an oxygen enriched water vapor.

45. The method of claim 43, wherein the oxidizing gas comprises a hydrogen enriched water vapor.