Silicon source reagent compositions, and method of making and using same for microelectronic device structure

Abstract

A method of synthesizing an aminosilane source reagent composition, by reacting an aminosilane precursor compound with an amine source reagent compound in a solvent medium comprising at least one activating solvent component, to yield an aminosilane source reagent composition having less than 1000 ppm halogen.

1 . A CVD precursor composition for forming a silicon-containing thin film on a substrate, said precursor composition including at least one aminosilane source reagent composition selected from the group consisting of:  
     
       
         
         
             
             
         
       
     
     wherein R 3  is selected from the group consisting of hydrogen, C 1 -C 4  alkyl, and C 1 -C 4  alkoxy; x is from 0 to 3; Si is silicon; A is halogen; y is from 0 to 3; N is nitrogen; each of R 1  and R 2  is same or different and is independently selected from the group consisting of H, aryl, perfluoroaryl, C 1 -C 8  alkyl, and C 1 -C 8  perfluoroalkyl; and n is from 1-6.  
   
   
       2 . The composition of  claim 1 , wherein said aminosilane source reagent composition is made by: 
 (a) reacting an aminosilane precursor compound with an amine source reagent compound, wherein the amine source reagent compound is selected from the group consisting of:                          wherein B is selected from the group consisting of H, Li, Na, K, Zn and MgBr; N is nitrogen; R 1  and R 2  are same or different and each is independently selected from the group consisting of H, aryl, perfluoroaryl, C 1 -C 8  alkyl, and C 1 -C 8  perfluoroalkyl; and n is from 1-6, in a solvent system comprising at least one non-polar solvent, at temperature in a range from about −30° C. to about room temperature, for a period of time sufficient to produce a reaction mixture comprising partially substituted aminosilane components, unreacted aminosilane precursors and unreacted amine components;    (b) combining the reaction mixture with at least one polar activating solvent component to at least partially solvate and activate the unreacted amine components, wherein the polar activating solvent comprises a Lewis base selected from the group consisting of ethers and tertiary amines; and    (c) continuing the reaction of step (b) at temperature in a range from about 0° C. to about 100° C. for a period of time sufficient to produce the aminosilane source reagent composition, wherein the aminosilane source reagent composition comprises less than 1000 ppm halogen.    
   
   
       3 . The CVD precursor composition according to  claim 2 , wherein the polar activating solvent is selected from the group consisting of: diethyl ether, tetrahydrofuran (THF), ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), 1,4-dioxane, tetraethylene glycol dimethyl ether (tetraglyme), 1,4,7,10-tetraoxacyclododecane (12-Crown-4), 1,4,7,10,13-pentaoxacyclopentadecane (15-Crown-5), and 1,4,7,10,13,16-hexaoxacyclooctadecane (18-Crown-6), pentamethyldiethylenetriamine (PMDETA), tetramethylethylene-diamine (TMEDA), Triethylamine; (TEA) Diazabicycloun-decene (DBU), Tri-n-butylamine (TNBA), and tetraethylethylenediamine (TEDA).  
   
   
       4 . The composition of  claim 1 , wherein said aminosilane source reagent composition is made by: 
 (1) combining an aminosilane precursor compound comprising at least one halogen leaving group, with an amine source reagent compound, in a solvent system comprising at least one non-polar solvent, for a period of time sufficient to produce a reaction mixture consisting essentially of partially substituted aminosilane components, unreacted aminosilane precursors and unreacted amine components;    (2) removing the non-polar solvent from the reaction mixture;    (3) combining with the reaction mixture of step (2) a polar activating solvent to at least partially solvate and activate the unreacted amine components;    (4) continuing the reaction of step (3) for a period of time sufficient to provide for essentially stoichiometric substitution of at least one halide on the aminosilane precursor compound by an amine component to produce the aminosilane source reagent composition.    
   
   
       5 . The method according to  claim 4 , wherein the non-polar solvent is removed by vacuum evaporation.  
   
   
       6 . The method according to  claim 4 , wherein the reaction of steps (2) and (3) is carried out at a temperature that is in the range of from about −30° C. to room temperature.  
   
   
       7 . The CVD precursor composition according to  claim 1 , further comprising at least one metalloamide source reagent composition selected from the group consisting of:  
     
       
         
         
             
             
         
       
     
     wherein M is selected from the group consisting of: Zr, Hf, Y, La, Lanthanide series elements, Ta, Ti, Al; N is nitrogen; each of R 1  and R 2  is same or different and is independently selected from the group consisting of H, aryl, perfluoroaryl, C 1 -C 8  alkyl, C 1 -C 8  perfluoroalkyl, alkylsilyl; x is the oxidation state on metal M; and n is from 1-6.  
   
   
       8 . The CVD precursor composition according to  claim 1 , further comprising at least one metalloamide source reagent composition having a formula:  
       M(NR 2 ) x (NR′ 2 ) y    
     wherein M is selected from the group consisting of: Y, Hf, La, and Ta; N is nitrogen, each of R and R′ is independently selected from the group consisting of H, aryl, perfluoroaryl, C 1 -C 8  alkyl, C 1 -C 8  perfluoroalkyl, and alkylsilyl; (NR 2 ) x  and (NR′ 2 ) y  are different amino ligands and R′ is different from R; x is from 1 to 5; y is from 1 to 5; and x+y is equal to the oxidation state of metal M, and a solvent medium, wherein the metalloamide source reagent compound is soluble or suspendable therein.  
   
   
       9 . The CVD precursor composition according to  claim 8 , wherein the solvent medium is selected from the group consisting of: ethers, glymes, tetraglymes, amines, polyamines, alcohols, glycols, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, cyclic ethers and combinations of two or more of the foregoing.  
   
   
       10 . A CVD method of forming a silicon-containing thin film on a substrate, comprising: 
 vaporizing the CVD precursor composition of  claim 1  to form a source reagent precursor vapor;    transporting the source reagent precursor vapor into a chemical vapor deposition zone, optionally using a carrier gas; and    contacting the source reagent precursor vapor with a substrate in said chemical vapor deposition zone at elevated temperature to deposit the silicon containing thin film on the substrate.    
   
   
       11 . A CVD method of forming a silicon-containing thin film on a substrate, comprising: 
 vaporizing the CVD precursor composition of  claim 8  to form a source reagent precursor vapor;    transporting the source reagent precursor vapor into a chemical vapor deposition zone, optionally using a carrier gas; and    contacting the source reagent precursor vapor with a substrate in said chemical vapor deposition zone at elevated temperature to deposit the silicon containing thin film on the substrate.    
   
   
       12 . A liquid CVD precursor composition for forming a silicon-containing thin film on a substrate, said precursor composition including 
 (a) at least one aminosilane source reagent composition selected from the group consisting of:                          wherein R 3  is selected from the group consisting of hydrogen, C 1 -C 4  alkyl, and C 1 -C 4  alkoxy; x is from 0 to 3; Si is silicon; A is halogen; y is from 0 to 3; N is nitrogen; each of R 1  and R 2  is same or different and is independently selected from the group consisting of H, aryl, perfluoroaryl, C 1 -C 8  alkyl, and C 1 -C 8  perfluoroalkyl; and n is from 1-6; and    (b) at least one metalloamide source reagent composition having a formula:      M(NR 2 ) x (NR′ 2 ) y      wherein M is selected from the group consisting of: Y, Hf, La, and Ta; N is nitrogen, each of R and R is independently selected from the group consisting of H, aryl, perfluoroaryl, C 1 -C 8  alkyl, C 1 -C 8  perfluoroalkyl, and alkylsilyl; (NR 2 ) x  and (NR′ 2 ) y  are different amino ligands and R′ is different from R; x is from 1 to 5; y is from 1 to 5; and x+y is equal to the oxidation state of metal M, and a solvent medium, wherein the metalloamide source reagent compound is soluble or suspendable therein.    
   
   
       13 . The CVD precursor composition according to  claim 9 , wherein the solvent medium is selected from the group consisting of: ethers, glymes, tetraglymes, amines, polyamines, alcohols, glycols, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, cyclic ethers and combinations of two or more of the foregoing.