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

Abstract

A CVD Method of forming gate dielectric thin films on a substrate using metalloamide compounds of the formula M(NR 1 R 2 ) x , wherein M is selected from the group consisting of: Zr, Hf, Y, La, Lanthanide series elements, Ta, Ti, Al; N is nitrogen; each of R1 and R2 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 and x is the oxidation state on metal M; and an aminosilane compound of the formula H x Si(NR 1 R 2 ) 4−x , wherein H is hydrogen; x is from 0 to 3; Si is silicon; N is nitrogen; each of R1 and R2 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. By comparison with the standard SiO 2 gate dielectric materials, these gate dielectric materials provide low levels of carbon and halide impurity. Also described is 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 liquid CVD precursor composition for forming a thin film dielectric on a substrate, such precursor composition including at least one metalloamide source reagent compound 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 1  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 ) 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.  
   
   
       2 . The liquid CVD precursor composition of  claim 1 , wherein the precursor composition further comprises an aminosilane source reagent compound of the formula:  
       H x Si(NR 1 R 2 ) 4−x    
     wherein H is hydrogen; x is from 0 to 3; Si is silicon; 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.  
   
   
       3 . The liquid CVD precursor composition of  claim 1 , wherein the CVD precursor composition further comprises a vapor source reagent compound selected from the group consisting of silane, trimethylsilane, tetramethylsilane, tetraethylorthosilicate.  
   
   
       4 . A CVD method of forming a dielectric thin film on a substrate, comprising: 
 vaporizing the liquid 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 a dielectric thin film on the substrate.    
   
   
       5 . The CVD method according to  claim 4 , wherein the liquid CVD precursor composition is vaporized in a liquid delivery apparatus.  
   
   
       6 . The CVD method according to  claim 4 , wherein the source reagent precursor vapor is transported into the chemical vapor deposition zone in a pulsed deposition mode.  
   
   
       7 . The CVD method according to  claim 4 , wherein the dielectric thin film is deposited in the absence of an oxidizer.  
   
   
       8 . The CVD method according to  claim 4 , wherein the liquid CVD precursor composition further comprises an aminosilane source reagent compound.  
   
   
       9 . The CVD method of  claim 8 , wherein the aminosilane source reagent compound has the formula:  
       H x Si(NR 1 R 2 ) 4−x    
     wherein H is hydrogen; x is from 0 to 3; Si is silicon; 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.  
   
   
       10 . The CVD method of  claim 4 , further comprising contacting the source reagent precursor vapor with the substrate in said chemical vapor deposition zone in the presence of an oxidizer at elevated temperature to form the dielectric thin film on the substrate.  
   
   
       11 . The CVD method according to  claim 10 , wherein the oxidizing gas is selected from the group consisting of: O 2 , N 2 O, NO and O 3 .  
   
   
       12 . The CVD method according to  claim 4 , wherein the chemical vapor deposition zone is at a temperature in the range of from about 350° C. to about 750° C.  
   
   
       13 . A method of forming a dielectric thin film on a substrate, comprising: 
 vaporizing a source reagent precursor composition mixture comprising the liquid CVD precursor composition of  claim 1  and at least one aminosilane precursor, to form a source reagent precursor vapor;    transporting the source reagent precursor vapor into a chemical vapor deposition zone, optionally using a carrier gas;    contacting the source reagent precursor vapor with a substrate in said chemical vapor deposition zone at elevated temperature to deposit a dielectric thin film on the substrate.    
   
   
       14 . A method of manufacturing a microelectronic device comprising a substrate having a dielectric thin film thereon, said method comprising: 
 vaporizing the liquid 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 a dielectric thin film on the substrate thereby forming said substrate having said dielectric thin film thereon.    
   
   
       15 . The method according to  claim 13 , wherein the liquid CVD precursor composition further comprises an aminosilane source reagent compound.  
   
   
       16 . The method of  claim 14 , wherein the aminosilane source reagent compound has the formula:  
       H x Si(NR 1 R 2 ) 4−x    
     wherein H is hydrogen; x is from 0 to 3; Si is silicon; 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.  
   
   
       17 . A method of synthesizing an aminosilane source reagent composition, comprising: 
 (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; 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.    
   
   
       18 . The method of  claim 17 , further comprising (d) separating the aminosilane source reagent composition from a by-product of the reaction mixture.  
   
   
       19 . The method of  claim 18 , further comprising (e) purifying the separated aminosilane source reagent composition.  
   
   
       20 . The method of  claim 19 , wherein the aminosilane source reagent composition is purified by distillation.  
   
   
       21 . The method of  claim 19 , further comprising (f) redissolving the purified aminosilane source reagent composition in a suitable solvent medium.  
   
   
       22 . The method of  claim 21 , wherein the suitable solvent medium comprises an organic solvent selected from the group consisting of ethers, glymes, tetraglymes, amines, polyamines, aliphatic hydrocarbons, aromatic hydrocarbons, cyclic ethers, and compatible combinations of two or more of the foregoing.  
   
   
       23 . A method of synthesizing an aminosilane source reagent composition, comprising the steps of: 
 (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) combining with the reaction mixture of step (1) a polar activating solvent to at least partially solvate and activate the unreacted amine components;    (3) continuing the reaction of step (2) 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, further comprising (4) separating the aminosilane source reagent composition from a by-product of the reaction mixture.    
   
   
       24 . The method of  claim 23 , further comprising (5) purifying the separated aminosilane source reagent composition.  
   
   
       25 . The method of  claim 24 , wherein the aminosilane source reagent composition is purified by distillation.  
   
   
       26 . The method of  claim 24 , further comprising (6) redissolving the purified aminosilane source reagent composition in a suitable solvent medium.  
   
   
       27 . The method of  claim 26 , wherein the suitable solvent medium comprises an organic solvent selected from the group consisting of ethers, glymes, tetraglymes, amines, polyamines, aliphatic hydrocarbons, aromatic hydrocarbons, cyclic ethers, and compatible combinations of two or more of the foregoing.  
   
   
       28 . A method of synthesizing an aminosilane source reagent composition, comprising the steps of: 
 (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, further comprising (5) separating the aminosilane source reagent composition from a by-product of the reaction mixture.    
   
   
       29 . The method of  claim 28 , further comprising (6) purifying the separated aminosilane source reagent composition.  
   
   
       30 . The method of  claim 29 , wherein the aminosilane source reagent composition is purified by distillation.  
   
   
       31 . The method of  claim 29 , further comprising (7) redissolving the purified aminosilane source reagent composition in a suitable solvent medium.  
   
   
       32 . The method of  claim 31 , wherein the suitable solvent medium comprises an organic solvent selected from the group consisting of ethers, glymes, tetraglymes, amines, polyamines, aliphatic hydrocarbons, aromatic hydrocarbons, cyclic ethers, and compatible combinations of two or more of the foregoing.  
   
   
       33 . The method according to  claim 17 , wherein the aminosilane source reagent composition is selected from the group consisting of: Si(NMe 2 ) 3 Cl, Si(NEt 2 ) 2 Cl 2 , Si(NMe 2 ) 4 , Si(NEt 2 ) 4  and Si(NMeEt) 4 .  
   
   
       34 . The method according to  claim 28 , wherein the aminosilane source reagent composition is selected from the group consisting of: Si(NMe 2 ) 3 Cl, Si(NEt 2 ) 2 Cl 2 , Si(NMe 2 ) 4 Si(NEt 2 ) 4  and Si(NMeEt) 4 .  
   
   
       35 . The method according to  claim 17 , wherein the aminosilane source reagent composition comprises Si(NMe 2 ) 4 .  
   
   
       36 . The method according to  claim 23 , wherein the aminosilane source reagent composition comprises Si(NMe 2 ) 4 .  
   
   
       37 . The method according to  claim 28 , wherein the aminosilane source reagent composition comprises Si(NMe 2 ) 4 .