Organometallic compounds and purification of such organometallic compounds
Disclosed herein are methods of purifying compounds useful for the deposition of high purity tin oxide and high purity compounds purified by those methods. Such compounds are those of the Formula as follows R x —Sn-A 4-x , wherein: A is selected from the group consisting of (Y a R′ z ) and a 3- to 7-membered N-containing heterocyclic group; each R group is independently selected from the group consisting of an alkyl or aryl group having from 1 to 10 carbon atoms; each R′ group is independently selected from the group consisting of an alkyl, acyl or aryl group having from 1 to 10 carbon atoms; x is an integer from 0 to 4; a is an integer from 0 to 1; Y is selected from the group consisting of N, O, S, and P; and z is 1 when Y is O, S or when Y is absent and z is 2 when Y is N or P.
1. A method purifying an organometallic compound comprising:
A) distilling in a first stage an organometallic compound of Formula 1:
R x —Sn-A 4-x Formula I
wherein:
each R group is independently selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms;
each R′ group is independently selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms;
x is an integer from 0 to 3;
wherein distilling in the first stage includes:
i) feeding feed material containing the first organometallic compound to a first distillation space at a reduced first pressure,
ii) heating the first distillation space to a first temperature to evaporate a portion of the feed material, and
iii) removing the evaporated portion of the feed material from the first distillation space such that a distillate is formed;
B) distilling, in at least one subsequent stage, the distillate from a previous stage,
wherein distilling the distillate from a previous stage includes:
i) feeding distillate from a previous stage to a subsequent distillation space at a reduced subsequent pressure,
ii) heating the subsequent distillation space to a subsequent temperature to evaporate a portion of the distillate from a previous stage,
iii) removing the evaporated portion of the distillate from a previous stage from the subsequent distillation space such that a subsequent distillate is formed; and
C) removing a final distillate from last of the subsequent stages, wherein step B is repeated a number of times at a reduced subsequent pressure sufficient to obtain the final distillate of the organometallic compound having purity as measured by nuclear magnetic resonance (NMR) spectroscopy of greater than 98%.
2. The method of claim 1 , wherein step B is repeated 1 to 19 times.
3. The method of claim 1 , wherein, in each subsequent stage, the distillation space has a subsequent pressure that is lower than a subsequent pressure in a previous stage.
4. The method of claim 3 , wherein, in each subsequent stage, a subsequent temperature is lower than a subsequent temperature in a previous stage.
5. The method of claim 1 , wherein, in each stage, the heating step is by steam in tubes and, in each subsequent stage, steam in the tubes is the evaporated portion of the feed material or distillate from a previous stage.
6. The method of claim 1 , wherein each R group is an independently selected alkyl group having from 1 to 4 carbon atoms.
7. The method of claim 1 , wherein each R′ group represents different alkyl groups.
8. The method of claim 1 , wherein the organometallic compound of Formula I is selected from the group consisting of Me 2 Sn(NMe 2 ) 2 , Me 2 Sn(NEtMe) 2 , t-BuSn(NEtMe) 3 , t-BuSn(NMe 2 ) 3 , t-BuSn(NEt 2 ) 3 , i-PrSn(NEtMe) 3 , i-PrSn(NEtMe 2 ) 3 , n-PrSn(NEtMe) 3 , n-PrSn(NEtMe 2 ) 3 , EtSn(NEtMe) 3 , i-BuSn(NEtMe) 3 , i-BuSn(NEtMe 2 ) 3 , n-BusSn(NMe 2 ) 3 , sec-BuSn(NMe 2 ) 3 , Et 2 Sn(NEtMe) 2 , Me 2 Sn(NEtMe) 2 , Sn(NMe 2 ) 4 , Sn(NEt 2 ) 4 , Sn(NEtMe) 4 , Bu 2 Sn(NEtMe) 2 , and Me 2 Sn(NEt 2 ) 2 .
9. The method of claim 8 , wherein the organometallic compound of Formula I is Sn(NMe 2 ) 4 .
10. The method of claim 1 , wherein at least one of the reduced first pressure and the reduced subsequent pressure are less than 10 −1 torr.
11. A method purifying an organometallic compound comprising:
A) distilling in a first stage an organometallic compound of Formula 1:
R x -Sn-(NR′ 2 ) 4−x Formula I
wherein:
each R group is independently selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms;
each R′ group is independently selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms;
x is an integer from 0 to 3;
wherein distilling in the first stage includes:
i) feeding feed material containing the first organometallic compound to a first distillation space at a reduced first pressure,
ii) heating the first distillation space to a first temperature to evaporate a portion of the feed material, and
iii) removing the evaporated portion of the feed material from the first distillation space such that a distillate is formed;
B) distilling, in at least one subsequent stage, the distillate from a previous stage,
wherein distilling the distillate from a previous stage includes:
i) feeding distillate from a previous stage to a subsequent distillation space at a reduced subsequent pressure,
ii) heating the subsequent distillation space to a subsequent temperature to evaporate a portion of the distillate from a previous stage,
iii) removing the evaporated portion of the distillate from a previous stage from the subsequent distillation space such that a subsequent distillate is formed; and
C) removing a final distillate from last of the subsequent stages, wherein step B is repeated a number of times at a reduced subsequent pressure sufficient to obtain the final distillate of the organometallic compound having a metal contamination of less than 1 ppm.
12. The method of claim 11 , wherein step B is repeated a number of times sufficient to reduce metal contamination to less than 100ppb.
13. The method of claim 12 , wherein step B is repeated a number of times sufficient to reduce metal contamination to 1ppb or less.
14. The method of claim 11 , wherein step B is repeated 1 to 19 times.
15. The method of claim 11 , wherein, in each subsequent stage, the distillation space has a subsequent pressure that is lower than a subsequent pressure in a previous stage.
16. The method of claim 15 , wherein, in each subsequent stage, a subsequent temperature is lower than a subsequent temperature in a previous stage.
17. The method of claim 11 , wherein, in each stage, the heating step is by steam in tubes and, in each subsequent stage, steam in the tubes is the evaporated portion of the feed material or distillate from a previous stage.
18. The method of claim 11 , wherein each R′ group represents different alkyl groups.
19. The method of claim 11 , wherein the organometallic compound of Formula I is selected from the group consisting of Me 2 Sn(NMe 2 ) 2 , Me 2 Sn(NEtMe) 2 , t-BuSn(NEtMe) 3 , t-BuSn(NMe 2 ) 3 , t-BuSn(NEt 2 ) 3 , i-PrSn(NEtMe) 3 , i-PrSn(NEtMe 2 ) 3 , n-PrSn(NEtMe) 3 , n-PrSn(NEtMe 2 ) 3 , EtSn(NEtMe) 3 , i-BuSn(NEtMe) 3 , i-BuSn(NEtMe 2 ) 3 , n-BusSn(NMe 2 ) 3 , sec-BuSn(NMe 2 ) 3 , Et 2 Sn(NEtMe) 2 , Me 2 Sn(NEtMe) 2 , Sn(NMe 2 ) 4 , Sn(NEt 2 ) 4 , Sn(NEtMe) 4 , Bu 2 Sn(NEtMe) 2 , and Me 2 Sn(NEt 2 ) 2 .
20. The method of claim 19 , wherein the organometallic compound of Formula I is Sn(NMe 2 ) 4 .
21. The method of claim 11 , wherein at least one of the reduced first pressure and the reduced subsequent pressure are less than 10 −1 torr.