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

• US 20050260347A1
• Filed: 05/21/2004
• Published: 11/24/2005
• Est. Priority Date: 05/21/2004
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Narwankar, Pravin K., Higashi, Gregg
• Granted Patent: US 8,119,210 B2
• Time in Patent Office: Days
• US Class Current: 427/248.100
• 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;

depositing a silicon-containing layer on the dielectric layer by an ALD process, comprising alternately pulsing a silicon precursor and an oxidizing gas into a process chamber;

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

exposing the substrate to an 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 from about 600°

C. to about 1,200°

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

4. The method of claim 3, wherein the capping layer is about 5 Å

or less.

5. The method of claim 1, wherein the dielectric layer is selected from the group consisting of HfO₂, HfSiO₄, HfSi_xO_yN_z, HfAl_xO_yN_z, Al₂O₃, HfO₂/Al₂O₃ laminate, LaAlO_x, LaO_x, 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 process chamber.

7. The method of claim 5, wherein the oxidizing gas comprises water formed by flowing a H₂ gas and an oxygen-containing gas through a water vapor generator.

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.

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

depositing the dielectric layer on a substrate;

exposing the dielectric layer to an ALD process, comprising alternately pulsing a silicon precursor and an oxidizing gas into the process chamber

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 oxidizing gas comprises water formed by flowing a H₂ gas and an oxygen-containing gas through a water vapor generator.

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 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 capping layer is about 5 Å

or less.

18. The method of claim 17, wherein the dielectric layer is selected from the group consisting of HfO₂, HfSiO₄, HfSi_xO_yN_z, HfAl_xO_yN_z, Al₂O₃, HfO₂/Al₂O₃ laminate, LaAlO_x, LaO_x, 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.

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

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.

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 from 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 is selected from the group consisting of HfO₂, HfSiO₄, HfSi_xO_yN_z, HfAl_xO_yN_z, Al₂O₃, HfO₂/Al₂O₃ laminate, LaAlO_x, LaO_x, derivatives 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 surface to a silicon precursor and an oxidizing gas comprising water formed by flowing a H₂ gas and an oxygen-containing gas through a water vapor generator; and

exposing the substrate surface 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-containing layer.

34. The method of claim 32, wherein the silicon-containing layer is about 5 Å

or less.

35. The method of claim 34, wherein the silicon-containing layer is deposited on a dielectric layer selected from the group consisting of HfO₂, HfSiO₄, HfSi_xO_yN_z, HfAl_xO_yN_z, Al₂O₃, HfO₂/Al₂O₃ laminate, LaAlO_x, LaO_x, derivatives thereof and combinations thereof.