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

Patent metadata

Field	Value
Publication number	US-11124876-B2
Application number	US-201916449070-A
Country	US
Kind code	B2
Filing date	Jun 21, 2019
Priority date	Mar 30, 2015
Publication date	Sep 21, 2021
Grant date	Sep 21, 2021

Abstract

Methods for halogenation of a hydrosilazane include contacting the hydrosilazane with a halogenating agent in a liquid phase to produce the halosilazane having a formula(SiHa(NR2)bXc)(n+2)Nn(SiH(2−d)Xd)(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 C1-C6 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 C1-C4 saturated or unsaturated hydrocarbyl group, a C1-C4 saturated or unsaturated alkoxy group, or an amino group [—NR1R2] with each R1 and R2 being further selected from H or a C1-C6 linear or branched, saturated or unsaturated hydrocarbyl group.

First claim

What is claimed is:

1. A Si-containing film forming composition comprising a halosilazane precursor
selected from the group consisting of (H 3 Si)N(SiH 2 Br) 2 , (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 (N i Pr 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) and (H 3 Si) 2 N(SiH 2 )N(SiH 3 )(SiH 2 I).

2. 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 halosilazane precursor

selected from the group consisting of (H 3 Si)N(SiH 2 Br) 2 , (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 (N i Pr 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); and
depositing at least part of the halosilazane precursor onto the substrate to form the silicon-containing film on the substrate using a vapor deposition process.

3. The method of claim 2 , further comprising the step of delivering into the reactor a co-reactant, wherein the co-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.

4. The method of claim 2 , further comprising the step of delivering into the reactor a second vapor including a second precursor, 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.

5. A method for halogenation of a hydrosilazane to produce a halosilazane, the methods comprising the step of
contacting the hydrosilazane with a halogenating agent in a liquid phase 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;
wherein the contacting step includes the steps of
adding the halogenating agent into a solvent to form a solution of the halogenating agent;
adding a catalyst to the solution of the halogenation agent, wherein the catalyst is a homogeneous catalyst selected from BPh 3 or B(SiMe 3 ) 3 or a heterogeneous catalyst selected from Ru, Pt or Pd in elemental form or deposited on an inert support surface.

6. The method of claim 5 , further comprising the steps of
mixing the solution of the halogenating agent with the hydrosilazane to form a mixture; and
separating the 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.

7. The method of claim 6 , further comprising the step of
stirring the mixture while monitoring the halogenation.

8. The method of claim 5 , wherein the molar ratio of the halogenating agent relative to the hydrosilazane is from 1 to 100% for selective synthesis of the halosilazane.

9. The method of claim 8 , wherein the halogenating agent is a trityl halide selected from Ph 3 CX (X═F, Cl, Br or I).

10. The method of claim 6 , wherein the solvent is selected from methylene chloride, chloroform, chloroethanes, chlorobenzenes, toluene, xylene, mesitylene, anisole, pentane, hexane, heptane, octane or mixtures thereof.

11. The method of claim 5 , wherein the temperature of the halogenation ranges from approximately 20° C. to approximately 200° C.

12. The method of claim 5 , wherein the pressure of the halogenation is from approximately 0 psig to approximately 50 psig.

13. The method of claim 5 , wherein a yield of halogenation of the hydrosilazane ranges from approximately 30% to approximately 90%.

14. The method of claim 5 , wherein a selectivity of halogenation of the hydrosilazane is up to approximately 97%.

15. The method of claim 5 , wherein each R is H and therefore 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.

16. The method of claim 5 , 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 (N i Pr 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