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

Patent metadata

Field	Value
Publication number	US-11820654-B2
Application number	US-202117409229-A
Country	US
Kind code	B2
Filing date	Aug 23, 2021
Priority date	Mar 30, 2015
Publication date	Nov 21, 2023
Grant date	Nov 21, 2023

Abstract

Methods for producing halosilazane comprise halogenating a hydrosilazane with a halogenating agent to produce the halosilazane, the halosilazane having a formula

(SiH a (NR 2 ) b X c ) (n+2) N n (SiH (2−d) X d ) (n−1) ,

wherein each a, b, c is independently 0 to 3; a+b+c=3; d is 0 to 2 and n≥1; wherein X is selected from a halogen atom selected from F, Cl, Br or I; each R is selected from H, a C 1 -C 6 linear or branched, saturated or unsaturated hydrocarbyl group, or a silyl group [SiR′ 3 ]; further wherein each R′ of the [SiR′ 3 ] is independently selected from H, a halogen atom selected from F, 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 1 R 2 ] with each R 1 and R 2 being further selected from H or a C 1 -C 6 linear or branched, saturated or unsaturated hydrocarbyl group, provided that when c=0, d≠0; or d=0, c≠0.

First claim

What is claimed is:

1. A method for producing halosilazane, the method comprising
halogenating a hydrosilazane with a trityl halide halogenating agent to produce the halosilazane, the halosilazane having a formula
(SiH a (NR 2 ) b X c ) (n+2) N n (SiH (2−d) X d ) (n−1) ,

wherein each a, b, c is independently 0 to 3; a+b+c=3; d is 0 to 2 and n≥1;
wherein X is selected from a halogen atom selected from F, Cl, Br or I; each R is selected from H, a C 1 -C 6 linear or branched, saturated or unsaturated hydrocarbyl group, or a silyl group [SiR′ 3 ]; further wherein each R′ of the [SiR′ 3 ] is independently selected from H, a halogen atom selected from F, 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 1 R 2 ] with each R 1 and R 2 being further selected from H or a C 1 -C 6 linear or branched, saturated or unsaturated hydrocarbyl group, provided that when c=0, d≠0; or d=0, c≠0, and
wherein the halogenating step includes the steps of
forming a mixture comprising the hydrosilazane, the halogenating agent;
adding a catalyst into the mixture; and
separating the formed halosilazane from the mixture, wherein the halosilazane is produced by selective halogenation of the hydrosilazane that has a general formula (SiH a (NR 2 ) b ) (n+2) N n (SiH 2 ) (n−1) , wherein each a, b, c is independently 0 to 3; a+b+c=3; d is 0 to 2 and n≥1; wherein X is selected from a halogen atom selected from F, Cl, Br or I; each R is selected from H, a C 1 -C 6 linear or branched, saturated or unsaturated hydrocarbyl group, or a silyl group [SiR′ 3 ]; further wherein each R′ of the [SiR′ 3 ] is independently selected from H, a halogen atom selected from F, 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 1 R 2 ] with each R 1 and R 2 being further selected from H or a C 1 -C 6 linear or branched, saturated or unsaturated hydrocarbyl group,
wherein a selectivity of halogenation of the hydrosilazane ranges from approximately 30% to approximately 100%.

2. The method of claim 1 , wherein the mixture includes a solvent.

3. The method of claim 1 , wherein the halogenating the hydrosilazane with the halogenating agent is in a liquid phase.

4. The method of claim 1 , wherein the molar ratio of the halogenating agent relative to the hydrosilazane is from 1 to 100% for selective synthesis of the halosilazane.

5. The method of claim 1 , wherein the trityl halide is selected from Ph 3 CF, Ph 3 CCl, Ph 3 CBr or Ph 3 Cl.

6. The method of claim 1 , wherein the trityl halide is Ph 3 CCI.

7. The method of claim 2 , wherein the solvent is selected from methylene chloride, chloroform, chloroethanes, chlorobenzenes, toluene, xylene, mesitylene, anisole, pentane, hexane, heptane, octane or mixtures thereof.

8. The method of claim 1 , wherein the catalyst is a homogeneous catalyst selected from BPh 3 or B(SiMe 3 ) 3 .

9. The method of claim 1 , wherein the catalyst is a heterogeneous catalyst selected from Ru, Pt or Pd in elemental form or deposited on an inert support surface.

10. The method of claim 1 , wherein the halogenating the hydrosilazane in the presence of the catalyst with the halogenating agent is in a liquid phase.

11. The method of claim 1 , wherein the temperature of the halogenation ranges from approximately 20° C. to approximately 200° C.

12. The method of claim 1 , wherein the pressure of the halogenation is from approximately 0 psig to approximately 50 psig.

13. The method of claim 1 , wherein a yield of halogenation of the hydrosilazane ranges from approximately 30% to approximately 90%.

14. The method of claim 1 , wherein a selectivity of halogenation of the hydrosilazane is up to approximately 97%.

15. The method of claim 1 , wherein each R is H.

16. The method of claim 15 , wherein the halosilazanes precursors are carbon-free halosilazanes precursors have a formula
(Si a H 2a+1 ) n+2−c (Si a H 2a+1−m X m ) c N n (SiH 2 ) (n−1−d) (SiH 2−b X b ) d ,

where X is selected from a halogen atom selected from F, Cl, Br or I; a, n≥1, 0<m<2a+1 and b=0-2, 0<c<n+2 and 0≤d<n−1.

17. The method of claim 1 , wherein the halosilazane is selected from (H 3 Si) 2 N(SiH 2 Cl), (H 3 Si)N(SiH 2 Br) 2 , (H 3 Si) 2 N(SiH 2 I), (H 3 Si)N(SiH 2 Cl) 2 , (H 3 Si)(H 2 SiCl)N(SiH 2 (N i Pr 2 )), (H 3 Si)(H 2 SiBr)N(SiH 2 (NiPr 2 )), (H 3 Si)(H 2 SiI)N(SiH 2 (N i Pr 2 )), (H 3 Si)(H 2 SiCl)N(SiH 2 (NEt 2 )), (H 3 Si)(H 2 SiBr)N(SiH 2 (NEt 2 )), (H 3 Si)(H 2 SiI)N(SiH 2 (NEt 2 )), (H 2 SiCl) 2 N(SiH 2 (N i Pr 2 )), (H 3 SiCl)N(SiH 2 (N i Pr 2 )) 2 , (H 2 SiCl)N(SiH 2 (NEt 2 )) 2 , (H 3 Si) 2 N(SiH 2 )N(SiH 3 )(SiH 2 Cl), (H 3 Si) 2 N(SiH 2 )N(SiH 3 )(SiH 2 Br) or (H 3 Si) 2 N(SiH 2 )N(SiH 3 )(SiH 2 I).

Assignees

• Air Liquide

Inventors

• Girard Jean-Marc
• Zhang Peng
• Sanchez Antonio
• Khandelwal Manish
• Itov Gennadiy
• Pesaresi Reno
• Nikiforov Grigory
• Orban David

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

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

• C23C16/45542

  Plasma being used non-continuously during the ALD reactions · CPC title

• H10P14/6336

  in the presence of a plasma [PECVD] · CPC title