Si-CONTAINING FILM FORMING PRECURSORS AND METHODS OF USING THE SAME

• US 20150376211A1
• Filed: 06/12/2015
• Published: 12/31/2015
• Est. Priority Date: 03/30/2015
• Status: Active Grant

• Current Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA), Volaix, LLC
• Original Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Inventors: ZHANG, Peng, GIRARD, Jean-Marc, SANCHEZ, Antonio, KHANDELWAL, Manish, ITOV, Gennadiy, PESARESI, Reno
• Granted Patent: US 9,777,025 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C01B 21/087 containing one or more hydrogen atoms
• CPC Class Codes: C01B 21/088 containing also one or more halogen atoms
• CPC Class Codes: C07F 7/025 without C-silicon linkages
• 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: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: C23C 16/515 using pulsed discharges
• CPC Class Codes: H01L 21/02164 the material being a silicon oxide, e.g. SiO2
• CPC Class Codes: H01L 21/02222 the compound being a silazane
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD

Abstract

Mono-substituted TSA precursor Si-containing film forming compositions are disclosed. The precursors have the formula: (SiH₃)₂N—SiH₂—X, wherein X is selected from a halogen atom; an isocyanato group; an amino group; an N-containing C₄-C₁₀ saturated or unsaturated heterocycle; or an alkoxy group. Methods for forming the Si-containing film using the disclosed mono-substituted TSA precursor are also disclosed.

Claims

1. A Si-containing film forming composition comprising a mono-substituted TSA precursor having the formula:

(SiH₃)₂N—

SiH₂—

X

wherein X is selected from a halogen atom selected from Cl, Br or I;

an isocyanato group [—

NCO];

an amino group [—

NR¹R²];

an N-containing C₄-C₁₀ saturated or unsaturated heterocycle;

or an alkoxy group [—

O—

R];

R¹, R² and R each is selected from H;

a C₁-C₆ linear or branched, saturated or unsaturated hydrocarbyl group;

or a silyl group [SiR′

₃] with each R′

being independently selected from H;

a halogen atom selected from Cl, Br, I;

a C₁-C₄ saturated or unsaturated hydrocarbyl group;

a C₁-C₄ saturated or unsaturated alkoxy group;

or an amino group [—

NR³R⁴] with each R³ and R⁴ being selected from H or a C₁-C₆ linear or branched, saturated or unsaturated hydrocarbyl group;

provided that if R¹═

H, then R²≠

H or Me.

2. The Si-containing film forming composition of claim 1, wherein X═

Cl.

3. The Si-containing film forming composition of claim 1, wherein X═

NR¹R² and R¹ and R² each is independently selected from H, Me, Et, or iPr.

4. The Si-containing film forming composition of claim 3, wherein the mono-substituted TSA precursor is (SiH₃)₂N—

SiH₂—

NiPr₂.

5. The Si-containing film forming composition of claim 3, wherein the mono-substituted TSA precursor is (SiH₃)₂N—

SiH₂—

NEt₂.

6. The Si-containing film forming composition of claim 3, wherein the mono-substituted TSA precursor is (SiH₃)₂N—

SiH₂—

NHiPr.

7. The Si-containing film forming composition of claim 1, wherein X is the N-containing C₄-C₁₀ saturated or unsaturated heterocycle selected from pyrrolidine, pyrrole, and piperidine.

8. The Si-containing film forming composition of claim 1, wherein X═

—

N(SiR₃)₂, and each R is independently selected from a halogen, H, or a C₁-C₄ alkyl group.

9. The Si-containing film forming composition of claim 8, wherein the mono-substituted TSA precursor is (SiH₃)₂N—

SiH₂—

N(SiH₃)₂.

10. The Si-containing film forming composition of claim 1, wherein X is —

O—

SiR₃, and each R is independently selected from H or a C₁-C₄ hydrocarbyl group.

11. The Si-containing film forming composition of claim 10, the precursor being (SiH₃)₂—

N—

SiH₂—

O—

SiMe.

12. A method for forming a Si-containing film, the method comprising the steps of:

introducing into a reactor containing a substrate a vapor including a mono-substituted TSA precursor having a formula (SiH₃)₂N—

SiH₂—

X, wherein X is selected from a halogen atom selected from Cl, Br or I;

an isocyanato group [—

NCO];

an amino group [—

NR¹R²];

a N-containing C₄-C₁₀ saturated or unsaturated heterocycle;

or an alkoxy group —

O—

R;

R¹, R² and R each is selected from H;

a C₁-C₆ linear or branched, saturated or unsaturated hydrocarbyl group;

or a silyl group SiR′

₃ with each R′

being independently selected from H;

a halogen atom selected from Cl, Br, or I;

a C₁-C₄ saturated or unsaturated hydrocarbyl group;

a C₁-C₄ saturated or unsaturated alkoxy group;

or an amino group NR³R⁴ with each R³ and R⁴ being selected from H or a C₁-C₆ linear or branched, saturated or unsaturated hydrocarbyl group, provided that if R¹═

H, then R²≠

H or Me;

depositing at least part of the mono-substituted TSA precursor onto the substrate to form the silicon-containing film on the substrate using a vapor deposition process.

13. The method of claim 12, wherein R¹ and R² each is independently selected from Me, Et, and iPr.

14. The method of claim 13, wherein the mono-substituted TSA precursor is (SiH₃)₂N—

SiH₂—

NiPr_2.

15. The method of claim 13, wherein the mono-substituted TSA precursor is (SiH₃)₂N—

SiH₂—

NEt₂.

16. The method of claim 13, wherein the mono-substituted TSA precursor is (SiH₃)₂N—

SiH₂—

NHiPr.

17. The method of claim 12, wherein X is the N-containing C₄-C₁₀ saturated or unsaturated heterocycle selected from pyrrolidine, pyrrole, and piperidine.

18. The method of claim 12, wherein X═

N(SiR₃)₂ and each R is independently selected from a halogen, H, or a C₁-C₄ alkyl group.

19. The method of claim 18, wherein the mono-substituted TSA precursor is (SiH₃)₂N—

SiH₂—

N(SiH₃)₂.

20. The method of claim 12, wherein X is —

O—

SiR₃ and each R is independently selected form H or a C₁-C₄ hydrocarbyl group.

21. The method of claim 12, wherein the vapor deposition process is atomic layer deposition or chemical vapor deposition.

22. The method of claim 12, further comprising the step of delivering into the reactor a reactant.

23. The method of claim 22, wherein the reactant is selected from the group consisting of O₂, O₃, H₂O, H₂O₂, NO, NO₂, N₂O, alcohols, diols, carboxylic acids, ketones, ethers, O atoms, O radicals, O ions, ammonia, N₂, N atoms, N radicals, N ions, saturated or unsaturated hydrazine, amines, diamines, ethanolamine, H₂, H atoms, H radicals, H ions, and combinations thereof.

24. The method of claim 12, further comprising the step of delivering into the reactor a second vapor including a second precursor.

25. The method of claim 24, wherein an element of the second precursor is selected from the group consisting of Ti, Hf, Zr, Ta, Nb, V, Al, Sr, Y, Ba, Ca, As, B, P, Sb, Bi, Sn, Ge, and combinations thereof.

26. The method of claim 12, wherein the substrate is selected from the group consisting of a silicon wafer, a glass substrate, and a plastic substrate.

27. The method of claim 26, wherein the substrate is coated with patterned or unpatterned organic or inorganic films.

28. The method of claim 23, further comprising the step of delivering into the reactor a second reactant, the second reactant being different than the reactant, the second reactant selected from the group consisting of O₂, O₃, H₂O, H₂O₂, NO, NO₂, N₂O, alcohols, diols, carboxylic acids, ketones, ethers, O atoms, O radicals, O ions, ammonia, N₂, N atoms, N radicals, N ions, saturated or unsaturated hydrazine, amines, diamines, ethanolamine, H₂, H atoms, H radicals, H ions, and combinations thereof.

29. A nitrogen-doped silicon oxide film, the film formed by the process of:

introducing into a reactor containing a substrate a vapor including a mono-substituted TSA precursor to form a silicon-containing layer on the substrate, the mono-substituted TSA precursor having a formula (SiH₃)₂N—

SiH₂—

X, wherein X is selected from a halogen atom selected from Cl, Br or I;

an isocyanato group [—

NCO];

an amino group [—

NR¹R²];

a N-containing C₄-C₁₀ saturated or unsaturated heterocycle;

or an alkoxy group [—

O—

R];

R¹, R² and R each is selected from H;

a C₁-C₆ linear or branched, saturated or unsaturated hydrocarbyl group;

or a silyl group SiR′

₃ with each R′

being independently selected from H;

a halogen atom selected from Cl, Br, or I;

a C₁-C₄ saturated or unsaturated hydrocarbyl group;

a C₁-C₄ saturated or unsaturated alkoxy group;

or an amino group —

NR³R⁴ with each R³ and R⁴ being selected from H or a C₁-C₆ linear or branched, saturated or unsaturated hydrocarbyl group, provided that if R¹═

H, then R²≠

H or Me;

reacting an oxidizing agent with the silicon-containing layer to form an oxidized silicon-containing layer by introducing the oxidizing agent into the reactor;

reacting the mono-substituted TSA precursor with the oxidized silicon-containing layer to form a silicon-rich oxidized silicon-containing layer by introducing the mono-substituted TSA precursor into the reactor;

reacting a nitrogen-containing reactant with the silicon-containing layer to form the nitrogen-doped silicon oxide film by introducing the nitrogen-containing reactant into the reactor.

30. The method of claim 29, further comprising purging the reactor with an inert gas between each introduction step.

31. The method of claim 29, wherein the mono-substituted TSA precursor is (SiH₃)₂N—

SiH₂—

NiPr_2.

32. The method of claim 29, wherein the mono-substituted TSA precursor is (SiH₃)₂N—

SiH₂—

NEt_2.

33. The method of claim 29, wherein the mono-substituted TSA precursor is (SiH₃)₂N—

SiH₂—

NHiPr.

34. The method of claim 29, wherein the mono-substituted TSA precursor is (SiH₃)₂N—

SiH₂—

N(SiH₃)₂.