Organoamino-Functionalized Cyclic Oligosiloxanes For Deposition Of Silicon-Containing Films

Abstract

Amino-functionalized cyclic oligosiloxanes, which have at least three silicon and three oxygen atoms as well as at least one organoamino group and methods for making the oligosiloxanes are disclosed. Methods for depositing silicon and oxygen containing films using the organoamino-functionalized cyclic oligosiloxanes are also disclosed.

1 . A composition comprising at least one organoamino-functionalized cyclic oligosiloxane compound selected from the group consisting of Formulae A-D: 
       
         
           
           
               
               
           
         
         wherein R 1  is selected from the group consisting of a linear C 1  to C 10  alkyl group, a branched C 3  to C 10  alkyl group, a C 3  to C 10  cyclic alkyl group, a C 3  to C 10  heterocyclic group, a C 3  to C 10  alkenyl group, a C 3  to C 10  alkynyl group, and a C 4  to C 10  aryl group; R 2  is selected from the group consisting of hydrogen, a C 1  to C 10  linear alkyl group, a branched C 3  to C 10  alkyl group, a C 3  to C 10  cyclic alkyl group, a C 3  to C 10  heterocyclic group, a C 3  to C 10  alkenyl group, a C 3  to C 10  alkynyl group, and a C 4  to C 10  aryl group, wherein R 1  and R 2  are either linked to form a cyclic ring structure or are not linked to form a cyclic ring structure; R 3-11  are each independently selected from the group consisting of hydrogen, a linear C 1  to C 10  alkyl group, a branched C 3  to C 10  alkyl group, a C 3  to C 10  cyclic alkyl group, a C 2  to C 10  alkenyl group, a C 2  to C 10  alkynyl group, a C 4  to C 10  aryl group, and an organoamino group, NR 1 R 2 , wherein R 1  and R 2  are defined above; n=1, 2, or 3, and m=2 or 3. 
       
     
     
         2 . The composition of  claim 1  further comprising at least one selected from the group consisting of a solvent and a purge gas. 
     
     
         3 . The composition of  claim 1  wherein each of R 3-9  is independently selected from the group consisting of hydrogen and a C 1  to C 4  alkyl group. 
     
     
         4 . The composition of  claim 1 , wherein R 1  is selected from the group consisting of a C 3  to C 10  cyclic alkyl group and a C 4  to C 10  aryl group. 
     
     
         6 . The composition of  claim 1 , wherein the composition is substantially free of one or more impurities selected from the group consisting of a halide, metal ions, metal, and combinations thereof. 
     
     
         7 . The composition of  claim 1 , wherein the organoamino-functionalized cyclic oligosiloxane compound is selected from the group consisting of: 2,4-bis(dimethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(dimethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(dimethylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(dimethylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-dimethylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(methylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(methylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(methylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(methylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-methylamino-2,4,6,8,10-pentamethylcyclopentasiloxane 2-methylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(iso-propylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(iso-propylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(iso-propylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(iso-propylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-iso-propylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-iso-propylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(N-ethylmethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(N-ethylmethylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-(N-ethylmethylamino)-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-(N-ethylmethylamino)-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(diethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(diethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(diethylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(diethylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-diethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-diethylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4,6-tris(dimethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetrakis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6-tris(methylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetrakis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane. 
     
     
         8 . A method for depositing a film comprising silicon and oxygen onto a substrate, the method comprising the steps of:
 a) providing a substrate in a reactor;   b) introducing into the reactor at least one silicon precursor compound selected from the group consisting of Formulae A-D   
       
         
           
           
               
               
           
         
         
           wherein R 1  is selected from the group consisting of a linear C 1  to C 10  alkyl group, a branched C 3  to C 10  alkyl group, a C 3  to C 10  cyclic alkyl group, a C 3  to C 10  heterocyclic group, a C 3  to C 10  alkenyl group, a C 3  to C 10  alkynyl group, and a C 4  to C 10  aryl group; R 2  is selected from the group consisting of hydrogen, a C 1  to C 10  linear alkyl group, a branched C 3  to C 10  alkyl group, a C 3  to C 10  cyclic alkyl group, a C 3  to C 10  heterocyclic group, a C 3  to C 10  alkenyl group, a C 3  to C 10  alkynyl group, and a C 4  to C 10  aryl group, wherein R 1  and R 2  are either linked to form a cyclic ring structure or are not linked to form a cyclic ring structure; R 3-11  are each independently selected from the group consisting of hydrogen, a linear C 1  to C 10  alkyl group, a branched C 3  to C 10  alkyl group, a C 3  to C 10  cyclic alkyl group, a C 2  to C 10  alkenyl group, a C 2  to C 10  alkynyl group, a C 4  to C 10  aryl group, and an organoamino group, NR 1 R 2 , wherein R 1  and R 2  are defined above; n=1, 2, or 3, and m=2 or 3; 
         
         c) purging the reactor with a purge gas; 
         d) introducing at least one of an oxygen-containing source and a nitrogen-containing source into the reactor; and 
         e) purging the reactor with the purge gas, 
         wherein the steps b through e are repeated until a desired thickness of film is deposited; 
         and wherein the method is conducted at one or more temperatures ranging from about 25° C. to 600° C. 
       
     
     
         9 . The method of  claim 8  wherein each of R 3-9  is independently selected from the group consisting of hydrogen and a C 1  to C 4  alkyl group. 
     
     
         10 . The method of  claim 8 , wherein R 1  is selected from the group consisting of a C 3  to C 10  cyclic alkyl group and a C 4  to C 10  aryl group. 
     
     
         11 . The method of  claim 8 , wherein the at least one silicon precursor compound is selected from the group consisting of 2,4-bis(dimethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(dimethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(dimethylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(dimethylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-dimethylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(methylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(methylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(methylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(methylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-methylamino-2,4,6,8,10-pentamethylcyclopentasiloxane 2-methylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(iso-propylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(iso-propylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(iso-propylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(iso-propylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-iso-propylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-iso-propylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(N-ethylmethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(N-ethylmethylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-(N-ethylmethylamino)-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-(N-ethylmethylamino)-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(diethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(diethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(diethylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(diethylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-diethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-diethylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4,6-tris(dimethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetrakis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6-tris(methylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetrakis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane. 
     
     
         12 . A silicon and oxygen containing film comprising at least one of the following characteristics: a density of at least about 2.1 g/cc; a wet etch rate that is less than about 2.5 Å/s as measured in a solution of 1:100 of HF to water dilute HF (0.5 wt % dHF) acid; an electrical leakage of less than about 1 e-8 A/cm 2  up to 6 MV/cm; and a hydrogen impurity of less than about 5 e20 at/cc as measured by Secondary Ion Mass Spectrometry (SIMS). 
     
     
         13 . A stainless steel container housing the composition of  claim 1 . 
     
     
         14 . The stainless steel container of  claim 13  further comprising an inert head-space gas selected from helium, argon, nitrogen and a combination thereof. 
     
     
         15 . The method of  claim 8  wherein the silicon precursor compound further comprising at least one selected from the group consisting of a solvent and an inert gas.