Organometallic compounds having sterically hindered amides

Abstract

This invention relates to organometallic compounds represented by the formula M(NR 1 R 2 ) x wherein M is a metal or metalloid, R 1 is the same or different and is a hydrocarbon group or a heteroatom-containing group, R 2 is the same or different and is a hydrocarbon group or a heteroatom-containing group; R 1 and R 2 can be combined to form a substituted or unsubstituted, saturated or unsaturated cyclic group; R 1 or R 2 of one (NR 1 R 2 ) group can be combined with R 1 or R 2 of another (NR 1 R 2 ) group to form a substituted or unsubstituted, saturated or unsaturated cyclic group; x is equal to the oxidation state of M; and wherein said organometallic compound has (i) a steric bulk sufficient to maintain a monomeric structure and a coordination number equal to the oxidation state of M with respect to anionic ligands, and (ii) a molecular weight sufficient to possess a volatility suitable for vapor deposition; a process for producing the organometallic compounds, and a method for producing a film or coating from organometallic precursor compounds.

1 . A process for the production of an organometallic compound comprising (i) reacting in a first pot a nitrogen-containing compound with an alkali metal, or an alkali metal-containing compound, or an alkaline earth metal, or an alkaline earth metal-containing compound, in the presence of a solvent and under reaction conditions sufficient to produce a first reaction mixture comprising a base material, (ii) adding said base material to a second pot containing a metal source compound and optionally an amine compound, (iii) reacting in said second pot said base material with said metal source compound and optionally said amine compound under reaction conditions sufficient to produce a second reaction mixture comprising said organometallic compound, and (iv) separating said organometallic compound from said second reaction mixture; wherein said organometallic compound is represented by the formula M(NR 1 R 2 ) x  wherein M is a metal or metalloid, R 1  is the same or different and is a hydrocarbon group or a heteroatom-containing group, R 2  is the same or different and is a hydrocarbon group or a heteroatom-containing group; R 1  and R 2  can be combined to form a substituted or unsubstituted, saturated or unsaturated cyclic group; R 1  or R 2  of one (NR 1 R 2 ) group can be combined with R 1  or R 2  of another (NR 1 R 2 ) group to form a substituted or unsubstituted, saturated or unsaturated cyclic group; x is equal to the oxidation state of M; and wherein said organometallic compound has (i) a steric bulk sufficient to maintain a monomeric structure and a coordination number equal to the oxidation state of M with respect to anionic ligands, and (ii) a molecular weight sufficient to possess a volatility suitable for vapor deposition. 
     
     
         2 . The process of  claim 1  wherein the metal source compound comprises a pure metal, a metal halide, or a metal pseudohalide. 
     
     
         3 . The process of  claim 1  wherein the metal source compound comprises La(CF 3 SO 3 ) 3 , LaCl 3 , LaBr 3 , LaI 3 , or SrCl 2 . 
     
     
         4 . The process of  claim 1  wherein the metal source compound comprises a lanthanide halide or a lanthanide trifluoromethanesulfonate. 
     
     
         5 . The process of  claim 1  wherein the base material comprises lithium diisopropylamide, lithium di-tert-amylamide, lithium tert-butylisopropylamide, lithium di-tert-butylamide, sodium di-tert-butylamide, lithium dicyclohexylamide, lithium tert-butyltrimethylsilylamide, or lithium bis(ethyldimethylsilyl)amide. 
     
     
         6 . The process of  claim 1  wherein the base material has a pKa greater than about 10. 
     
     
         7 . The process of  claim 1  wherein the amine compound comprises diisopropylamine, di-tert-amylamine, tert-butylisopropylamine, di-tert-butylamine, dicyclohexylamine, tert-butyltrimethylsilylamine, or diethyltetramethyldisilazane. 
     
     
         8 . The process of  claim 1  wherein the organometallic compound yield is 60% or greater. 
     
     
         9 . A method for producing a film, coating or powder by decomposing an organometallic precursor compound represented by the formula M(NR 1 R 2 ) x  wherein M is a metal or metalloid, R 1  is the same or different and is a hydrocarbon group or a heteroatom-containing group, R 2  is the same or different and is a hydrocarbon group or a heteroatom-containing group; R 1  and R 2  can be combined to form a substituted or unsubstituted, saturated or unsaturated cyclic group; R 1  or R 2  of one (NR 1 R 2 ) group can be combined with R 1  or R 2  of another (NR 1 R 2 ) group to form a substituted or unsubstituted, saturated or unsaturated cyclic group; x is equal to the oxidation state of M; and wherein said organometallic compound has (i) a steric bulk sufficient to maintain a monomeric structure and a coordination number equal to the oxidation state of M with respect to anionic ligands, and (ii) a molecular weight sufficient to possess a volatility suitable for vapor deposition; thereby producing the film, coating or powder. 
     
     
         10 . The method of  claim 9  wherein the decomposing of said organometallic precursor compound is thermal, chemical, photochemical or plasma-activated. 
     
     
         11 . The method of  claim 9  wherein said organometallic precursor compound is vaporized and the vapor is directed into a deposition reactor housing a substrate. 
     
     
         12 . The method of  claim 11  wherein said substrate is comprised of a material selected from the group consisting of a metal, a metal silicide, a metal aluminate, a semiconductor, an insulator and a barrier material. 
     
     
         13 . The method of  claim 11  wherein said substrate is a patterned wafer. 
     
     
         14 . The method of  claim 9  wherein said film, coating or powder is produced by a gas phase deposition. 
     
     
         15 . The method of  claim 9  wherein said film, coating or powder is produced by a chemical vapor deposition or atomic layer deposition.