Si-containing film forming compositions and methods of making and using the same

Patent metadata

Field	Value
Publication number	US-11407922-B2
Application number	US-201716087464-A
Country	US
Kind code	B2
Filing date	Mar 23, 2017
Priority date	Mar 23, 2016
Publication date	Aug 9, 2022
Grant date	Aug 9, 2022

Abstract

Si-containing film forming compositions are disclosed comprising a precursor having the formula [—NR—R4R5Si—(CH2)t—SiR2R3—]n wherein n=2 to 400; R, R2, R3, R4, and R5 are independently H, a hydrocarbon group, or an alkylamino group, and provided that at least one of R2, R3, R4, and R5 is H; and R is independently H, a hydrocarbon group, or a silyl group. Exemplary pre-cursors include, but are not limited to, [—NH—SiH2—CH2—SiH2—]n, and [—N(SiH2—CH2—SiH3)—SiH2—CH2—SiH2—]n.

First claim

We claim:

1. A Si-containing film forming composition comprising a linear or branched oligomer or polymer containing a unit having the formula:
[—NR—R 4 R 5 Si—(CH 2 ) t —SiR 2 R 3 —] n   (II)

wherein t=1 to 4; n=2 to 400;
R 2 , R 3 , R 4 , and R 5 are independently H, a C 1 to C 6 hydrocarbon, or an alkylamino group having the formula NR″ 2 and each R″ is independently H, a C 1 -C 6 hydrocarbon, a C 6 -C 12 aryl, or NR″ 2 forms a cyclic amine group,
and provided that at least one of R 2 , R 3 , R 4 , and R 5 is H; and
R is H; a C 1 -C 6 hydrocarbon; a silyl group having the formula Si x R′ 2x+1 , with x=1 to 4 and each R′ is independently H, a C 1 -C 6 hydrocarbon group, or an alkylamino group having the formula NR″ 2 and each R″ is independently H, a C 1 -C 6 group, a C 6 -C 12 aryl, or NR″ 2 forms a cyclic amine group; or a R 1′ R 2′ Si(CH 2 ) b Si R 3′ R 4′ R 5′ group, with b=1 to 2 and R 1′ , R 2′ , R 3′ , R 4′ , and R 5′ are independently a H, a C 1 -C 6 hydrocarbon, a C 6 -C 12 aryl, or an alkylamino group having the formula NR″ 2 and each R″ is independently H, a C 1 -C 6 group, a C 6 -C 12 aryl, or NR″ 2 forms a cyclic amine group; and provided that at least one of R 1′ , R 2′ , R 3′ , R 4′ , and R 5′ is H; and
further wherein the oligomer or polymer has a molecular weight of 500 to 1,000,000 daltons.

2. The Si-containing film forming composition of claim 1 , wherein the linear or branched oligomer or polymer contains a unit having the formula [—NH—SiH 2 —(CH 2 ) t —SiH 2 —] n , with t=1-2.

3. The Si-containing film forming composition of claim 1 , wherein the linear or branched oligomer or polymer contains a unit having a formula selected from the group consisting of:
[—N(SiH 3 )—SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(Si 2 H 5 )—SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(Si 3 H 7 )—SiH 2 —(CH 2 ) t —SiH 2 —] n ,and
[—N(Si 4 H 9 )—SiH 2 —(CH 2 ) t —SiH 2 —] n , with t=1-2.

4. The Si-containing film forming composition of claim 1 , wherein the linear or branched oligomer or polymer contains a unit having a formula selected from the group consisting of
[—N(Si(Me) 3 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(Si(Et) 3 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(Si(iPr) 3 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(Si(nPr) 3 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(Si(Bu) 3 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(Si(iBu) 3 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(Si(tBu) 3 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(Si(amyl) 3 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(Si(hexyl) 3 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH(Me) 2 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH(Et) 2 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH(iPr) 2 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH(nPr) 2 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH(Bu) 2 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH(iBu) 2 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH(tBu) 2 )-SiH 2 —(CH 2 )t—SiH 2 —] n ,
[—N(SiH(amyl) 2 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH(hexyl) 2 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH 2 (Me))-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH 2 (Et))-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH 2 (iPr))-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH 2 (nPr))-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH 2 (nBu))-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH 2 (iBu))-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH 2 (tBu))-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH 2 (amyl))-SiH 2 —(CH 2 ) t —SiH 2 —] n , and
[—N(SiH 2 (hexyl))-SiH 2 —(CH 2 ) t —SiH 2 —] n , with t=1-2.

5. The Si-containing film forming composition of claim 1 , wherein the linear or branched oligomer or polymer contains a unit having a formula selected from the group consisting of
[—N(SiH 2 —CH 2 —SiH 3 )—SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiMe 2 —CH 2 —CH 2 —SiMe 3 )—SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiEt 2 —CH 2 —SiEt 3 )—SiH 2 —(CH 2 ) t —SiH 2 —] n , and
[—N(SiEt 2 —CH 2 —CH 2 —SiEt 3 )—SiH 2 —(CH 2 ) t —SiH 2 —] n , with t=1-2.

6. The Si-containing film forming composition of claim 1 , wherein the linear or branched oligomer or polymer contains a unit having a formula selected from the group consisting of
[—N(Me)-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(Et)-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(iPr)-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(nPr)-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(Bu)-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(iBu)-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(tBu)-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(amyl)-SiH 2 —(CH 2 ) t —SiH 2 —] n , and
[—N(hexyl)-SiH 2 —(CH 2 ) t —SiH 2 —] n , with t=1-2.

7. The Si-containing film forming composition of claim 1 , wherein the linear or branched oligomer or polymer contains a unit having a formula selected from the group consisting of
[—N(SiH 2 NMe 2 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH 2 NEt 2 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH 2 NiPr 2 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH 2 NnPr 2 )-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH 2 NMeEt)-SiH 2 —(CH 2 ) t —SiH 2 —] n ,
[—N(SiH(NMe 2 ) 2 )-SiH 2 —(CH 2 ) t —SiH 2 —] n , and
[—N(SiH(NEt 2 ) 2 )-SiH 2 —(CH 2 ) t —SiH 2 —] n , with t=1-2.

8. The Si-containing film forming composition of claim 1 , wherein the oligomer or polymer has a molecular weight of 1,000 to 100,000 daltons.

9. The Si-containing film forming composition of claim 1 , wherein the oligomer or polymer has a molecular weight of 3,000 to 50,000 daltons.

10. The Si-containing film forming composition of claim 1 , wherein the linear or branched oligomer or polymer contains a unit having a formula selected from the group consisting of
[—NH—SiH 2 —(CH 2 ) t —SiH(CH═CH 2 )—] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(CH 2 —CH═CH 2 )—] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NH 2 )—] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NMe 2 )-] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NMeEt)-] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NEt 2 )-] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NnPr 2 )-] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NiPr 2 )-] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NnBu 2 )-] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NiBu 2 )-] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NtBu 2 )-] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NAmyl 2 )-] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(Ncyclopentyl 2 )-] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(Nhexyl 2 )-] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(Ncyclohexyl 2 )-] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NMeH)—] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NEtH)—] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NnPrH)—] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NiPrH)—] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NnBuH)—] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NiBuH)—] n ,
[—NH—SiH 2 —(CH 2 ) t —SiH(NtBuH)—] n , and
[—NH—SiH 2 —(CH 2 ) t —SiH(NAmylH)—] n .

11. The Si-containing film forming composition of claim 1 , wherein the linear or branched oligomer or polymer contains a unit having a formula selected from the group consisting of
[—NH—SiH 2 —(CH 2 ) t —Si(CH═CH 2 ) 2 —] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(CH 2 —CH═CH 2 ) 2 —] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NH 2 ) 2 —] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NMe 2 ) 2 -] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NMeEt) 2 -] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NEt 2 ) 2 -] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NnPr 2 ) 2 -] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NiPr 2 ) 2 -] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NnBu 2 ) 2 -] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NiBu 2 ) 2 -] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NtBu 2 ) 2 -] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NAmyl 2 ) 2 -] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(Ncyclopentyl 2 ) 2 -] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(Si(Nhexyl 2 ) 2 -] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(Ncyclohexyl 2 ) 2 -] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NMeH) 2 —] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NEtH) 2 —] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NnPrH) 2 —] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NiPrH) 2 —] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NnBuH) 2 —] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NiBuH) 2 —] n ,
[—NH—SiH 2 —(CH 2 ) t —Si(NtBuH) 2 —] n , and
[—NH—SiH 2

Assignees

• Air Liquide American
• Air Liquide
• Khandelwal Manish
• Kerrigan Sean
• Girard Jean Marc
• Sanchez Antonio
• Zhang Peng
• Wang Yang

Inventors

• Khandelwal Manish
• Kerrigan Sean
• Girard Jean-Marc
• Sanchez Antonio
• Zhang Peng
• Wang Yang

Classifications

• C08G77/60

  in which all the silicon atoms are connected by linkages other than oxygen atoms · CPC title

• C07F7/10 Primary

  containing nitrogen {having a Si-N linkage} · CPC title

• C09D183/16 Primary

  in which all the silicon atoms are connected by linkages other than oxygen atoms · CPC title

• C08G77/70

  Siloxanes defined by use of the MDTQ nomenclature · CPC title

• C08G77/62

  Nitrogen atoms · CPC title