Composition and method for low temperature deposition of silicon-containing films such as films including silicon nitride, silicon dioxide and/or silicon-oxynitride

• US 20040096582A1
• Filed: 11/14/2002
• Published: 05/20/2004
• Est. Priority Date: 11/14/2002
• Status: Active Grant

• Current Assignee: Entegris Incorporated
• Original Assignee: Advanced Technology Materials, Inc. (Entegris Incorporated)
• Inventors: Xu, Chongying, Laxman, Ravi K., Baum, Thomas H., Wang, Ziyun, Hendrix, Bryan, Roeder, Jeffrey
• Granted Patent: US 7,531,679 B2
• Time in Patent Office: Days
• US Class Current: 427/255.27
• CPC Class Codes: C07F 7/025 without C-silicon linkages
• CPC Class Codes: C07F 7/10 containing nitrogen having a Si-N linkage
• CPC Class Codes: C07F 7/12 Organo silicon halides
• CPC Class Codes: C23C 16/308 Oxynitrides
• CPC Class Codes: C23C 16/345 Silicon nitride
• CPC Class Codes: C23C 16/402 Silicon dioxide
• CPC Class Codes: C30B 25/02 Epitaxial-layer growth
• CPC Class Codes: C30B 29/06 Silicon
• CPC Class Codes: H01L 21/0217 the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz H01L21/02126 and H01L21/0214 take precedence
• CPC Class Codes: H01L 21/02219 the compound comprising silicon and nitrogen
• CPC Class Codes: H01L 21/02222 the compound being a silazane
• 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 21/3144 on silicon
• CPC Class Codes: H01L 21/31612 on a silicon body
• CPC Class Codes: H01L 21/3185 of siliconnitrides

Abstract

Silicon precursors for forming silicon-containing films in the manufacture of semiconductor devices, such as low dielectric constant (k) thin films, high k gate silicates, low temperature silicon epitaxial films, and films containing silicon nitride (Si₃N₄), siliconoxynitride (SiO_xN_y) and/or silicon dioxide (SiO₂). The precursors of the invention are amenable to use in low temperature (e.g., <500° C.) chemical vapor deposition processes, for fabrication of ULSI devices and device structures.

Claims

1. A silicon compound selected from the group consisting of:

(A) compounds of the formula;

[SiX_n(NR¹R²)_3-n]₂ 

 

(1)

 

wherein;

R¹ and R² may be the same as or different from one another and each is independently selected from the group consisting of H, C₁-C₅ alkyl, and C₃-C₆ cycloalkyl;

X is selected from the group consisting of halogen, hydrogen and deuterium; and

0≦

n≦

2;

(B) compounds of the formula (2)

 

wherein;

each of R₃ can be the same as or different from the other and each is independently selected from the group consisting of H, C₁-C₄ alkyl, and C₃-C₆ cycloalkyl; and

each of R₄, R₅ and R₆ can be the same as or different from the others and each is independently selected from the group consisting of H, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, Si(CH₃)₃ and SiCl₃;

(C) metal source reagent complexes formed by metal cation reaction with deprotonated anionic forms of the compounds (B);

(D) disilicon cycloamides of the formulae (3)-(6);

 

wherein;

each of R₈ can be the same as or different from the others and each is independently selected from the group consisting of H, C₁-C₄ alkyl, and C₃-C₆ cycloalkyl; and

each of R₉ can be the same as or different from the others and each is independently selected from the group consisting of H and NR₈H where R₈ is as defined above; and

(E) cyclosilicon compounds of the formula;

wherein;

each of R₁₀ and R₁₁ can be the same as or different from the others and each is independently selected from the group consisting of H, C₁-C₄ alkyl, and C₃-C₆ cycloalkyl.

17. A method of forming a silicon-containing film on a substrate, comprising contacting a substrate under chemical vapor deposition conditions including temperature below 600°

C. with a vapor of a silicon compound as in claim 1.

18. The method of claim 17, wherein the silicon compound is of formula (1).

19. The method of claim 18, wherein the silicon-containing film comprises a material selected from the group consisting of silicon oxide, silicon oxynitride and silicon and said temperature is <

500°

C.

20. The method of claim 19, wherein the silicon-containing compound is selected from the group consisting of (Et₂N)₂ClSi—

SiCl(NEt₂)₂, (EtNH)₃Si—

Si(HNEt)₃, (Bu^tNH)₂ClSi—

SiCl(HNBu^t)₂, (Me₂N)₂ClSi—

SiCl(NMe₂)₂, Cl₂HSi—

SiHCl₂, and (EtNH)₂HSi—

SiH(NHEt)₂.

21. The method of claim 19, wherein the silicon-containing compound comprises a compound of the formula:

22. The method of claim 17, wherein the silicon compound comprises a compound of formula (2).

23. The method of claim 17, wherein the silicon compound is selected from those of the group consisting of compounds of formulae (3)-(6).

24. The method of claim 17, wherein the silicon compound comprises a compound of formula (7).

25. The method of claim 17, wherein said silicon-containing film comprises a film selected from the group consisting of films comprising silicon, silicon nitride (Si₃N₄), siliconoxynitride (SiO_xN_y), silicon dioxide (SiO₂), low dielectric constant (k) thin silicon-containing films, high k gate silicate films and low temperature silicon epitaxial films.

26. The method of claim 17, wherein said chemical vapor deposition conditions comprise temperature of from about 400 to about 625°

C., pressure of from about 10 to about 100 torr, and the presence of ammonia.

27. The method of claim 17, wherein said chemical vapor deposition conditions comprise temperature of from about 525 to about 625°

C., pressure of from about 0.1 to about 10 torr.

28. The method of claim 17, comprising depositing oxynitride deposition of silicon.

29. The method of claim 17, comprising depositing oxynitride deposition of silicate.

31. The method of claim 17, wherein the silicon-containing film comprises silicon nitride.

32. The method of claim 17, wherein said temperature is <

500°

C.

34. A method of forming a metal, metal nitride or metal oxide film on a substrate, comprising contacting said substrate with a precursor metal complex formed by ionic reaction of metal cation with a deprotonated compound formed by deprotonation reaction of a silicon compound of formula (2) as in claim 1.

35. The method of claim 34, wherein said silicon compound has the formula:

36. The method of claim 34, wherein the metal cation comprises cation of a metal selected from the group consisting of hafnium, zirconium and barium.

37. The method of claim 17, wherein the silicon compound comprises a disilicon cycloamide compound.

38. The method of claim 17, wherein the silicon compound comprises a precursor reacted with a co-reactant in a reaction scheme selected from the group consisting of those of reaction scheme (C) below:

39. The method of claim 38, wherein the silicon compound comprises (NEt₂)ClSi—

SiCl(NEt₂).

2. A silicon compound of the formula

[SiX_n(NR¹R²)_3-n]₂ 

 

(1)

 

wherein;

R¹ and R² may be the same as or different from one another and each is independently selected from the group consisting of H, C₁-C₅ alkyl, and C₃-C₆ cycloalkyl;

X is selected from the group consisting of halogen, hydrogen and deuterium; and

0≦

n≦

2.

3. The silicon compound of claim 2, selected from the group consisting of (Et₂N)₂ClSi—

SiCl(NEt₂)₂, (EtNH)₃Si—

Si(HNEt)₃, (Bu^tNH)₂ClSi—

SiCl(HNBu^t)₂, (Me₂N)₂ClSi—

SiCl(NMe₂)₂, Cl₂HSi—

SiHCl₂, and (EtNH)₂HSi—

SiH(NHEt)₂.

4. The silicon compound of claim 2, of the formula:

5. A silicon compound of the formula (2):

6. The silicon compound according to claim 5, selected from the group consisting of compounds of the formula:

7. The silicon compound of claim 6, wherein both R substituents are hydrogen.

8. The silicon compound of claim 6, wherein both R substituents are methyl.

9. The silicon compound of claim 6, of the formula (2a).

10. The silicon compound of claim 6, comprising a metal source reagent complex formed by metal cation reaction with a deprotonated anionic form of a compound of formula (2a).

11. The silicon compound of claim 10, wherein the metal cation comprises a cation of a transition metal.

12. The silicon compound of claim 10, wherein the metal cation comprises a cation of a metal selected from the group consisting of hafnium (Hf), zirconium (Zr), and barium (Ba).

13. A silicon compound selected from the group consisting of disilicon cycloamides of the formulae (3)-(6):

14. A cyclosilicon compound of the formula:

15. The silicon compound of claim 14, wherein each of R₁₀ and R₁₁ is tertiary butyl (Bu^t).

16. (NEt₂)₂ClSi—

SiCl(NEt₂)₂.

33. A method of making a compound of the formula:

[SiX_n(NR¹R²)_3-n]₂ 

 

(1)

wherein;

R¹ and R² may be the same as or different from one another and each is independently selected from the group consisting of H, C₁-C₅ alkyl, and C₃-C₆ cycloalkyl;

X is selected from the group consisting of halogen, hydrogen and deuterium; and

0≦

n≦

2,

said method comprising reacting a disilane compound of the formula X₃Si—

SiX₃ with an amine (R¹R²NH) or lithium amide ((R¹R²N)Li compound, wherein X, R¹ and R² are as set out above, according to a reaction selected from the group consisting of the following reactions;

wherein each of the R substituents may be the same as or different from the other and each is independently selected from the group consisting of H, C₁-C₄ alkyl, and C₃-C₆ cycloalkyl.

40. A method of forming a silicon nitride film on a substrate by chemical vapor deposition, comprising contacting said substrate with vapor of silicon source and nitrogen source compounds, wherein said nitrogen source compounds are other than nitrogen or ammonia, and said chemical vapor deposition is conducted at temperature <

550°

C., wherein said nitrogen source compound is selected from the group consisting of R-diazo compounds, wherein R is H, C₁-C₄ alkyl or C₃-C₆ cycloalkyl, triazoles, tetrazoles, amadines, silylazides, small ring nitrogen compounds, and molecules including organic acyclic or cyclic moieties that contain one or more —

N—

N bonds.

41. The method of claim 40, wherein said small ring nitrogen compounds are selected from the group consisting of aziridines.

42. A method of forming a silicon epitaxial layer on a substrate at temperature below about 600°

C., by contacting the substrate with a silicon precursor in the presence of a substantial excess of a reducing agent.

43. The method of claim 42, wherein said reducing agent comprises an agent selected from the group consisting of hydrogen, silane (SiH₄) and disilane (Si₂H₆).

44. The method of claim 43, wherein the temperature is below about 550°

C.