Compositions and methods for depositing silicon nitride films
Described herein are compositions, silicon nitride films and methods for forming silicon nitride films using at least on cyclodisilazane precursor. In one aspect, there is provided a method of forming a silicon nitride film comprising the steps of: providing a substrate in a reactor; introducing into the reactor an at least one cyclodisilazane comprising a hydrocarbon leaving group and two Si—H groups wherein the at least one cyclodisilazane reacts on at least a portion of the surface of the substrate to provide a chemisorbed layer; purging the reactor with a purge gas; introducing a plasma comprising nitrogen and an inert gas into the reactor to react with at least a portion of the chemisorbed layer and provide at least one reactive site wherein the plasma is generated at a power density ranging from about 0.01 to about 1.5 W/cm 2 .
1. A method of forming a silicon nitride film onto at least a surface of a substrate, the method comprising
a. providing a substrate in a reactor;
b. introducing into the reactor a cyclodisilazane precursor comprising a leaving hydrocarbon group and at least two Si—H groups and selected from the group consisting of 1,3-bis(tert-butyl)cyclodisilazane, 1,3-bis(tert-butyl)-2-methylcyclodisilazane, 1,3-bis(tert-butyl)-2,4-dimethylcyclodisilazane, 1,3-bis(tert-amyl)cyclodisilazane, 1,3-bis(tert-amyl)-2-methylcyclodisilazane, 1,3-bis(tert-amyl)-2,4-dimethylcyclodisilazane, 1,3-bis(tert-butyl)-2-chloroclodisilazane, 1,3-bis(tert-butyl)-2,4-dichlorocyclodisilazane, 1,3-bis(tert-amyl)-2-chloroclodisilazane, 1,3-bis(tert-amyl)-2,4-dichlorocyclodisilazane, 1,3-bis(tert-butyl)-2,4,4-trilchlorocyclodisilazane, 1,3-bis(tert-butyl)-2-dimethylcyclodisilazane, 1,3-bis(tert-butyl)-2-chloro-2-methylcyclodisilazane, 1,3-bis(tert-amyl)-2-dimethylcyclodisilazane, 1,3-bis(tert-amyl)-2-chloro-2-methyl-cyclodisilazane, 1,3-bis(tert-butyl)-2-vinylcyclodisilazane, 1,3-bis(tert-butyl)-2-ethynylcyclodisilazane and combinations thereof, wherein the at least one cyclodisilazane reacts on at least a portion of the surface of the substrate to provide a chemisorbed layer;
c. purging the reactor with a purge gas;
d. introducing a plasma containing source and an inert gas into the reactor to react with at least a portion of the chemisorbed layer and provide at least one reactive site wherein the plasma is generated at a power density ranging from about 0.01 to about 1.5 W/cm 2 ; and
e. optionally purging the reactor with an inert gas; and wherein the steps b through e are repeated until a desired thickness of the silicon nitride film is obtained.
2. The method of claim 1 the plasma containing source is selected from the group consisting of a nitrogen/argon plasma, ammonia plasma, nitrogen/ammonia plasma, ammonia/helium plasma, ammonia/argon plasma, ammonia/nitrogen plasma, NF 3 plasma, organoamine plasma, and mixtures thereof.
3. The method of claim 1 wherein the silicon nitride film has a density of 2.2 g/cc or greater.
4. The method of claim 1 wherein the method is a vapor deposition process and is selected from the group consisting of at least one selected from plasma enhanced chemical vapor deposition and plasma enhanced cyclic chemical vapor deposition.
5. The method of claim 1 wherein the method is conducted at one or more temperatures of about 400° C. or less.
6. The method of claim 1 wherein the method is conducted at one or more temperatures of about 300° C. or less.
7. The method of claim 1 wherein step b further comprises introducing a noble gas into the reactor.
8. A method of forming a silicon nitride film onto at least a surface of a substrate, the method comprising the steps of:
a. providing a substrate in a reactor;
b. introducing into the reactor at least one cyclodisilazane precursor selected from the group consisting of 1,3-bis(tert-butyl)cyclodisilazane, 1,3-bis(tert-butyl)-2-methylcyclodisilazane, 1,3-bis(tert-butyl)-2,4-dimethylcyclodisilazane, 1,3-bis(tert-amyl)cyclodisilazane, 1,3-bis(tert-amyl)-2-methylcyclodisilazane, 1,3-bis(tert-amyl)-2,4-dimethylcyclodisilazane, 1,3-bis(tert-butyl)-2-chloroclodisilazane, 1,3-bis(tert-butyl)-2,4-dichlorocyclodisilazane, 1,3-bis(tert-amyl)-2-chloroclodisilazane, 1,3-bis(tert-amyl)-2,4-dichlorocyclodisilazane, 1,3-bis(tert-butyl)-2,4,4-trilchlorocyclodisilazane, 1,3-bis(tert-butyl)-2-dimethylcyclodisilazane, 1,3-bis(tert-butyl)-2-chloro-2-methylcyclodisilazane, 1,3-bis(tert-amyl)-2-dimethylcyclodisilazane, 1,3-bis(tert-amyl)-2-chloro-2-methyl-cyclodisilazane, 1,3-bis(tert-butyl)-2-vinylcyclodisilazane, 1,3-bis(tert-butyl)-2-ethynylcyclodisilazane and combinations thereof wherein the at least one cyclodisilazane reacts on at least a portion of the surface of the substrate to provide a chemisorbed layer;
c. purging the reactor with a purge gas comprising at least one selected from nitrogen, a noble gas, and combinations thereof;
d. introducing a plasma containing source into the reactor to react with at least a portion of the chemisorbed layer and provide an at least one reactive site wherein the plasma is generated at a power density ranging from about 0.01 to about 1.5 W/cm 2 ; and
e. optionally purge the reactor with an inert gas; and wherein the steps b through e are repeated until a desired thickness of the silicon nitride film is obtained.
9. The method of claim 8 wherein the silicon nitride film has a density of 2.2 g/cc or greater.
10. The method of claim 8 wherein method is a vapor deposition process selected from the group consisting of plasma enhanced chemical vapor deposition and plasma enhanced cyclic chemical vapor deposition.
11. The method of claim 8 wherein the method is conducted at a temperature of 400° C. or less.
12. The method of claim 8 wherein the method is conducted at a temperature of 300° C. or less.
13. The method of claim 8 where the plasma containing source is selected from the group consisting of a nitrogen/argon plasma, ammonia plasma, nitrogen/ammonia plasma, ammonia/helium plasma, ammonia/argon plasma, ammonia/nitrogen plasma, NF 3 plasma, organoamine plasma, and mixtures thereof.
14. The method of claim 8 wherein step b further comprises introducing a noble gas into the reactor.
15. The method of claim 8 wherein a plasma comprising hydrogen can be inserted before step d to help remove hydrocarbon generated from the reaction between the cyclodisilazane and the surface.
16. The method of claim 15 wherein the plasma comprising hydrogen is selected from the group consisting of hydrogen plasma, hydrogen/helium, hydrogen/argon plasma, hydrogen/neon plasma and mixtures thereof.
17. A method of forming a silicon aluminum nitride film onto at least a surface of a substrate, the method comprising the steps of:
a. providing a substrate in a reactor;
b. introducing into the reactor at least one cyclodisilazane precursor selected from the group consisting of 1,3-bis(tert-butyl)cyclodisilazane, 1,3-bis(tert-butyl)-2-methylcyclodisilazane, 1,3-bis(tert-butyl)-2,4-dimethylcyclodisilazane, 1,3-bis(tert-amyl)cyclodisilazane, 1,3-bis(tert-amyl)-2-methylcyclodisilazane, 1,3-bis(tert-amyl)-2,4-dimethylcyclodisilazane, 1,3-bis(tert-butyl)-2-chloroclodisilazane, 1,3-bis(tert-butyl)-2,4-dichlorocyclodisilazane, 1,3-bis(tert-amyl)-2-chloroclodisilazane, 1,3-bis(tert-amyl)-2,4-dichlorocyclodisilazane, 1,3-bis(tert-butyl)-2,4,4-trilchlorocyclodisilazane, 1,3-bis(tert-butyl)-2-dimethylcyclodisilazane, 1,3-bis(tert-butyl)-2-chloro-2-methylcyclodisilazane, 1,3-bis(tert-amyl)-2-dimethylcyclodisilazane, 1,3-bis(tert-amyl)-2-chloro-2-methyl-cyclodisilazane, 1,3-bis(tert-butyl)-2-vinylcyclodisilazane, 1,3-bis(tert-butyl)-2-ethynyl cyclodisilazane and combinations thereof wherein the at least one cyclodisilazane reacts on at least a portion of the surface of the substrate to provide a chemisorbed layer;
c. purging the reactor with a purge gas comprising at least one selected from nitrogen, a noble gas, and combinations thereof;
d. introducing a first plasma containing source into the reactor to react with at least a portion of the chemisorbed layer and provide an at least one reactive site wherein the plasma is generated at a power density ranging from about 0.01 to about 1.5 W/cm 2 ; and
e. optionally purging the reactor with an inert gas;
f) introducing into the reactor at least one aluminum precursor selected from the group consisting of AlCl 3 , trimethylaluminum, triethylaluminum, and tris(dimethylamino)aluminum,
g) purging the reactor using inert gas,
h) introducing a second plasma containing source into the reactor wherein the plasma is generated at a power density ranging from about 0.01 to about 1.5 W/cm 2 , and
i) optionally purging the reactor using inert gas,
wherein the steps b through i are repeated until a desired thickness of the silicon aluminum nitride film is obtained.
18. The method of claim 17 wherein the silicon aluminum nitride film has a density of 2.2 g/cc or greater.
19. The method of claim 17 wherein method is a vapor deposition process selected from the group consisting of at least one selected from plasma enhanced chemical vapor deposition and plasma enhanced cyclic chemical vapor deposition.
20. The method of claim 17 wherein the method is conducted at a temperature of 400° C. or less.
21. The method of claim 17 wherein each of the plasma containing sources is individually selected from the group consisting of a nitrogen/argon plasma, ammonia plasma, nitrogen/ammonia plasma, ammonia/helium plasma, ammonia/argon plasma, ammonia/nitrogen plasma, NF 3 plasma, organoamine plasma, and mixtures thereof.