Perhydropolysilazane compositions and methods for forming oxide films using same
A Si-containing film forming composition comprising a catalyst and/or a polysilane and a N—H free, C-free, and Si-rich perhydropolysilazane having a molecular weight ranging from approximately 332 dalton to approximately 100,000 dalton and comprising N—H free repeating units having the formula [—N(SiH3)x(SiH2-)y], wherein x=0, 1, or 2 and y=0, 1, or 2 with x+y=2; and x=0, 1 or 2 and y=1, 2, or 3 with x+y=3. Also disclosed are synthesis methods and applications for using the same.
1. A Si-containing film forming composition comprising
a) a catalyst and/or a polysilane, and
b) a N—H free, C-free, and Si-rich perhydropolysilazane having a molecular weight ranging from approximately 332 dalton to approximately 100,000 dalton and comprising N—H free repeating units having the formula [—N(SiH 3 ) x (SiH 2 -) y ], wherein x=0, 1, or 2 and y=0, 1, or 2 with x+y=2; and x=0, 1 or 2 and y=1, 2, or 3 with x+y=3.
2. The Si-containing film forming composition of claim 1 , wherein the N—H free, C-free, and Si-rich perhydropolysilazane has a Si:N ratio ranging from approximately 1.5:1 to approximately 2.5:1.
3. The Si-containing film forming composition of claim 1 , wherein the N—H free, C-free, and Si-rich perhydropolysilazane has no —Si(—)(H)— and a SiH 2 :SiH 3 ratio ranging from approximately 1 to approximately 5.
4. The Si-containing film forming composition of claim 1 , wherein the catalyst is selected from the group consisting of a desilylative coupling catalyst, a dehydrocoupling catalyst and both a desilylative coupling catalyst and a dehydrocoupling catalyst.
5. The Si-containing film forming composition of claim 4 , wherein the dehydrocoupling catalyst having the formula ML 4 , with M being a Group IV or Group V element and each L independently being selected from the group consisting of NR 2 , OR, R 5 Cp, R—N—C(R″)=N—R′, beta-diketonate, iminoketonate, diiminate, and combinations thereof, with R, R′ and R″ independently being H, a C 1 -C 4 hydrocarbon, or a trialkylsilyl group.
6. The Si-containing film forming composition of claim 4 , wherein the catalyst is selected from a metal carbonyl or a metal carbonyl containing molecule, the metal being selected from Co, Ni, Ru, Fe, Rh, Os.
7. The Si-containing film forming composition of claim 4 , wherein the catalyst is Co 2 (CO) 8 .
8. The Si-containing film forming composition of claim 1 , comprising the polysilane.
9. The Si-containing film forming composition of claim 1 , wherein the Si-containing film forming composition comprises the catalyst.
10. The Si-containing film forming composition of claim 8 , wherein the polysilane has a formula
Si x H (2x+2) ,
wherein x ranges from approximately 4 to approximately 50, preferably from approximately 10 to approximately 40, and more preferably from approximately 15 to approximately 30, or a formula
Si n H 2n+1−m (NR 2 ) m ,
where each R independently H or a C 1 -C 4 hydrocarbon; m is 1 or 2; and n ranges from approximately 3 to approximately 50.
11. A method of forming a Si-containing film on a substrate, the method comprising contacting the Si-containing film forming composition of claim 1 with the substrate via a spin coating, spray coating, dip coating, or slit coating technique to form the Si-containing film.
12. The method of claim 11 , wherein the substrate comprises trenches having an aspect ratio ranging from approximately 1:1 to approximately 1:100.
13. The method of claim 11 , further comprising exposing the Si-containing film at a temperature ranging from approximately 30° C. to 200° C.
14. The method of claim 13 , further comprising exposing the Si-containing film to an oxidizing atmosphere comprising at least one of O 2 , O 3 , H 2 O 2 , H 2 O, N 2 O, or NO at a temperature ranging from 200° C. to 1000° C.
15. A Si-containing film forming composition comprising
a) a catalyst and/or a polysilane, and
b) a N—H free, C-free, and Si-rich perhydropolysilazane having a molecular weight ranging from approximately 500 dalton to approximately 1,000,000 dalton and comprising N—H free repeating units having the formula [—N(SiH 3 ) x (SiH 2 -) y ], wherein x=0, 1, or 2 and y=0, 1, or 2 with x+y=2; and x=0, 1 or 2 and y=1, 2, or 3 with x+y=3.
16. The Si-containing film forming composition of claim 15 , wherein the molecular weight ranges from approximately 1,000 daltons to approximately 200,000 daltons.
17. The Si-containing film forming composition of claim 15 , wherein the molecular weight ranges from approximately 3,000 daltons to approximately 100,000 daltons.