Si-containing film forming precursors and methods of using the same

Patent metadata

Field	Value
Publication number	US-9777025-B2
Application number	US-201514738039-A
Country	US
Kind code	B2
Filing date	Jun 12, 2015
Priority date	Mar 30, 2015
Publication date	Oct 3, 2017
Grant date	Oct 3, 2017

Abstract

Mono-substituted TSA precursor Si-containing film forming compositions are disclosed. The precursors have the formula: (SiH 3 ) 2 N—SiH 2 —X, wherein X is selected from a halogen atom; an isocyanato group; an amino group; an N-containing C 4 -C 10 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.

First claim

What is claimed is:

1. A Si-containing film forming composition comprising a mono-substituted TSA precursor having the formula:
(SiH 3 ) 2 N—SiH 2 —X

wherein X is selected from an isocyanato group [—NCO]; an amino group [—NR 1 R 2 ]; an N-containing C 4 -C 10 saturated or unsaturated heterocycle; or an alkoxy group [—O—R]; R 1 , R 2 and R each is selected from H; a C 1 -C 6 linear or branched, saturated or unsaturated hydrocarbyl group; provided that if R 1 ═H, then R 2 ≠H or Me.

2. The Si-containing film forming composition of claim 1 , wherein X═NR 1 R 2 and R 1 and R 2 each is independently selected from H, Me, Et, or iPr.

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

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

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

6. The Si-containing film forming composition of claim 1 , wherein X is —O—SiR 3 , and each R is independently selected from H or a C 1 -C 4 hydrocarbyl group.

7. The Si-containing film forming composition of claim 6 , the precursor being (SiH 3 ) 2 —N—SiH 2 —O—SiMe 3 .

8. 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 (SiH 3 ) 2 N—SiH 2 —X, wherein X is selected from a an isocyanato group [—NCO]; an amino group [—NR 1 R 2 ]; a N-containing C 4 -C 10 saturated or unsaturated heterocycle; or an alkoxy group —O—R; R 1 , R 2 and R each is selected from H; a C 1 -C 6 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 C 1 -C 4 saturated or unsaturated hydrocarbyl group; a C 1 -C 4 saturated or unsaturated alkoxy group; or an amino group —NR 3 R 4 with each R 3 and R 4 being selected from H or a C 1 -C 6 linear or branched, saturated or unsaturated hydrocarbyl group, provided that if R 1 ═H, then R 2 ≠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.

9. The method of claim 8 , wherein R 1 and R 2 each is independently selected from Me, Et, and iPr.

10. The method of claim 9 , wherein the mono-substituted TSA precursor is (SiH 3 ) 2 N—SiH 2 —NiPr 2 .

11. The method of claim 9 , wherein the mono-substituted TSA precursor is (SiH 3 ) 2 N—SiH 2 —NEt 2 .

12. The method of claim 9 , wherein the mono-substituted TSA precursor is (SiH 3 ) 2 N—SiH 2 —NHiPr.

13. The method of claim 8 , wherein X is —O—SiR 3 and each R is independently selected form H or a C 1 -C 4 hydrocarbyl group.

14. The method of claim 8 , wherein the vapor deposition process is atomic layer deposition or chemical vapor deposition.

15. The method of claim 8 , further comprising the step of delivering into the reactor a reactant.

16. The method of claim 15 , wherein the reactant is selected from the group consisting of O 2 , O 3 , H 2 O, H 2 O 2 , NO, NO 2 , N 2 O, alcohols, diols, carboxylic acids, ketones, ethers, O atoms, O radicals, O ions, ammonia, N 2 , N atoms, N radicals, N ions, saturated or unsaturated hydrazine, amines, diamines, ethanolamine, H 2 , H atoms, H radicals, H ions, and combinations thereof.

17. The method of claim 8 , further comprising the step of delivering into the reactor a second vapor including a second precursor.

18. The method of claim 17 , 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.

19. The method of claim 8 , wherein the substrate is selected from the group consisting of a silicon wafer, a glass substrate, and a plastic substrate.

20. The method of claim 19 , wherein the substrate is coated with patterned or unpatterned organic or inorganic films.

21. The method of claim 16 , 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 O 2 , O 3 , H 2 O, H 2 O 2 , NO, NO 2 , N 2 O, alcohols, diols, carboxylic acids, ketones, ethers, O atoms, O radicals, O ions, ammonia, N 2 , N atoms, N radicals, N ions, saturated or unsaturated hydrazine, amines, diamines, ethanolamine, H 2 , H atoms, H radicals, H ions, and combinations thereof.

22. 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 (SiH 3 ) 2 N—SiH 2 —X, wherein X is selected from a halogen atom selected from Cl, Br or I; an isocyanato group [—NCO]; an amino group [—NR 1 R 2 ]; a N-containing C 4 -C 10 saturated or unsaturated heterocycle; or an alkoxy group [—O—R]; R 1 , R 2 and R each is selected from H; a C 1 -C 6 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 C 1 -C 4 saturated or unsaturated hydrocarbyl group; a C 1 -C 4 saturated or unsaturated alkoxy group; or an amino group —NR 3 R 4 with each R 3 and R 4 being selected from H or a C 1 -C 6 linear or branched, saturated or unsaturated hydrocarbyl group, provided that if R 1 ═H, then R 2 ≠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.

23. The method of claim 22 , further comprising purging the reactor with an inert gas between each introduction step.

24. The method of claim 22 , wherein the mono-substituted TSA precursor is (SiH 3 ) 2 N—SiH 2 —NiPr 2 .

25. The method of claim 22 , wherein the mono-substituted TSA precursor is (SiH 3 ) 2 N—SiH 2 —NEt 2 .

26. The method of claim 22 , wherein the mono-substituted TSA precursor is (SiH 3 ) 2 N—SiH 2 —NHiPr.

27. The method of claim 22 , wherein the mono-substituted TSA precursor is (SiH 3 ) 2 N—SiH 2 —N(SiH 3 ) 2 .

Assignees

• L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude
• L'Air Liquide Société Pour L'Etude Et L'Exploitation Des Procédés Georges Claude

Inventors

• Girard Jean-Marc
• Zhang Peng
• Sanchez Antonio
• Khandelwal Manish
• Itov Gennadiy
• Pesaresi Reno

Classifications

• H10P14/69215

  the material being a silicon oxide, e.g. SiO2 · CPC title

• H10P14/6689

  the compound being a silazane · CPC title

• H10P14/6339 Primary

  deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD · CPC title

• C23C16/345

  Silicon nitride · CPC title

• C07F7/025 Primary

  without C-silicon linkages · CPC title