Process for preparing higher halosilanes and hydridosilanes
View Patent ↗The invention relates to a process for preparing higher halosilanes by disproportionation of lower halosilanes. The invention further relates to a process for preparing higher hydridosilanes from the higher halosilanes prepared by disproportionation. The invention further relates to mixtures containing at least one higher halosilane or at least one higher hydridosilane prepared by the process described. Finally, the invention relates to the use of such a mixture containing at least one higher hydridosilane for producing electronic or optoelectronic component layers or for producing silicon-containing layers.
1. A process for preparing a higher halosilane, the process comprising:
converting at least one halosilane of formula:
Si n X 2n+2 ,
by disproportionation to a product mixture comprising at least one higher halosilane of formula:
Si m X 2m+2 , and
at least one lower halosilane of formula:
Si a X 2a+2 ,
wherein n is equal to or larger than 2;
m is larger than n;
a is 1 or 2; and
X is F, Cl, Br, I, or a combination thereof, and
wherein a reaction is catalysed by at least one tertiary phosphine,
wherein the at least one halosilane is selected from the group consisting of Si 2 X 6 , Si 3 X 8 , and Si 4 X 10 .
2. The process according to claim 1 , wherein the at least one tertiary phosphine is at least one selected from the group consisting of a tertiary alkylphosphine, a tertiary arylphosphine, and a tertiary bidentate phosphine.
3. The process according to claim 2 , wherein the at least one tertiary phosphine is at least one selected from the group consisting of trimethylphosphine, triethylphosphine, and triphenylphosphine.
4. The process according to claim 1 , wherein the at least one halosilane is a linear silane.
5. The process according to claim 1 , further comprising:
hydrogenating the at least one higher halosilane, thereby obtaining the at least one higher hydridosilane of formula Si m H 2m+2 .
6. The process according to claim 5 , further comprising:
removing the at least one lower halosilane from the product mixture prior to the hydrogenating.
7. The process according to claim 5 , wherein the hydrogenating is effected by adding at least one hydrogenating agent selected from the group consisting of a metal hydride of a metal of main groups 1 to 3 and a hydridic compound comprising LiAlH 4 , NaBH 4 , or iBu 2 AlH.
8. The process according to claim 7 , wherein the hydrogenating agent is present in a 2- to 30-fold molar excess of the at least one halosilane added.
9. The process according to claim 6 , wherein the removing is distillative removing or drawing off at a temperature of from −30 to +100° C. and a pressure of from 0.01 to 1013 mbar prior to the hydrogenating.
10. The process according to claim 8 , wherein the hydrogenating agent is present in a 10- to 15-fold molar excess of the at least one halosilane added.
11. A method for producing at least one higher halosilane, comprising:
producing the at least one higher halosilane with at least one tertiary phosphine.
12. The method according to claim 11 , wherein the at least one tertiary phosphine is at least one selected from the group consisting of a tertiary alkylphosphine, a tertiary arylphosphine, and a tertiary bidentate phosphine.
13. The process according to claim 1 , which is conducted at room temperature.