Processes for the production of organometallic compounds

Abstract

This invention relates to processes for the production of organometallic compounds represented by the formula M(L) 3 wherein M is a Group VIII metal, e.g., ruthenium, and L is the same or different and represents a substituted or unsubstituted amidinato group or a substituted or unsubstituted amidinato-like group, which process comprises (i) reacting a substituted or unsubstituted metal source compound, e.g., ruthenium (II) compound, with a substituted or unsubstituted amidinate or amidinate-like compound in the presence of a solvent and under reaction conditions sufficient to produce a reaction mixture comprising said organometallic compound, e.g., ruthenium (III) compound, and (ii) separating said organometallic compound from said reaction mixture. The organometallic compounds are useful in semiconductor applications as chemical vapor or atomic layer deposition precursors for film depositions.

1 . A process for the production of an organometallic compound selected from the following: 
 (1) a process for the production of an organometallic compound represented by the formula (L) 2 M(L′) 2  which process comprises (i) reacting a substituted or unsubstituted metal source compound represented by the formula MX 2 R with a substituted or unsubstituted amidinate or amidinate-like compound represented by the formula A 1 L and a ligand source represented by the formula L′, in the presence of a solvent and under reaction conditions sufficient to produce a reaction mixture comprising said organometallic compound, and (ii) separating said organometallic compound from said reaction mixture; and    (2) a process for the production of an organometallic compound represented by the formula M(L) 3  which process comprises (i) reacting a substituted or unsubstituted metal source compound represented by the formula MX 2 R with a substituted or unsubstituted amidinate or amidinate-like compound represented by the formula A 1 L in the presence of a solvent and under reaction conditions sufficient to produce a reaction mixture comprising said organometallic compound, and (ii) separating said organometallic compound from said reaction mixture;    wherein M is a Group VIII metal, X is a halogen group, R is a substituted or unsubstituted hydrocarbon group, Al is an alkali metal, L is the same or different and represents a substituted or unsubstituted amidinato group or a substituted or unsubstituted amidinato-like group, and L′ is the same or different and represents N 2  or a substituted or unsubstituted heteroatom-containing group.    
   
   
       2 . The process of  claim 1  wherein, in the metal source compound represented by the formula MX 2 R, M is Ru, Os or Fe, X is fluoro, chloro, bromo or iodo, and R is η 6 -benzene or η 6 -toluene.  
   
   
       3 . The process of  claim 1  wherein the metal source compound is selected from bis[dichloro(η 6 -benzene)ruthenium (II)] and bis[dichloro(η 6 -toluene)ruthenium (II)].  
   
   
       4 . The process of  claim 1  wherein, in the amidinate or amidinate-like compound represented by the formula A 1 L, A 1  is lithium, sodium or bromium and L is an amidinato group or a negatively charged, chelating, four electron donor group.  
   
   
       5 . The process of  claim 1  wherein the amidinate or amidinate-like compound is selected from lithium (N,N′-diisopropylacetamidinate), lithium (N,N′-diisopropylformamidinate), lithium (N,N′-di-n-propylacetamidinate), lithium (N,N′-di-n-propylformamidinate), lithium (N,N′-diethylacetamidinate), lithium (N,N′-diethylformamidinate), lithium (N,N′-dimethylacetamidinate), and lithium (N,N′-dimethylformamidinate).  
   
   
       6 . The process of  claim 1  wherein the ligand source represented by the formula L′ is selected from N 2 , CO, NCR 7 , PR 7 R 8 R 9  or NR 7 R 8 R 9 , wherein R 7 , R 8  and R 9  are the same or different and each represents hydrogen, a halogen atom, an acyl group having from 1 to about 12 carbon atoms, an alkoxy group having from 1 to about 12 carbon atoms, an alkoxycarbonyl group having from 1 to about 12 carbon atoms, an alkyl group having from 1 to about 12 carbon atoms, an amine group having from 1 to about 12 carbon atoms or a silyl group having from 0 to about 12 carbon atoms.  
   
   
       7 . The process of  claim 1  wherein the organometallic compound produced by process (1) comprises bis(N,N′-diisopropylacetamidinato)bis(dinitrogen)ruthenium (II), bis(N,N′-diisopropylacetamidinato)dicarbonylruthenium (II), bis(N,N′-diisopropylacetamidinato)di-trimethylphosphineruthenium (II), bis(N,N′-diisopropylformamidinato)bis(dinitrogen)ruthenium (II), bis(N,N′-diisopropylformamidinato)dicarbonylruthenium (II), bis(N,N′-diisopropylfonnamidinato)di-trimethylphosphineruthenium (II), bis(N,N′-di-n-propylacetamidinato)bis(dinitrogen)ruthenium (II), bis(N,N′-di-n-propylacetamidinato)dicarbonylruthenium (II), bis(N,N′-di-n-propylacetamidinato)di-trimethylphosphineruthenium (II), bis(N,N′-di-n-propylformamidinato)bis(dinitrogen)ruthenium (II), bis(N,N′-di-n-propylformamidinato)dicarbonylruthenium (II), bis(N,N′-di-n-propylformamidinato)di-trimethylphosphineruthenium (II), bis(N,N′-diethylacetamidinato)bis(dinitrogen)ruthenium (II), bis(N,N′-diethylacetamidinato)dicarbonylruthenium (II), bis(N,N′-diethylacetamidinato)di-trimethylphosphineruthenium (II), bis(N,N′-diethylformamidinato)bis(dinitrogen)ruthenium (II), bis(N,N′-diethylformamidinato)dicarbonylruthenium (II), bis(N,N′-diethylformamidinato)di-trimethylphosphineruthenium (II), bis(N,N′-dimethylacetamidinato)bis(dinitrogen)ruthenium (II), bis(N,N′-dimethylacetamidinato)dicarbonylruthenium (II), bis(N,N′-dimethylacetamidinato)di-trimethylphosphineruthenium (II), bis(N,N′-dimethylformamidinato)bis(dinitrogen)ruthenium (II), bis(N,N′-dimethylformamidinato)dicarbonylruthenium (II), or bis(N,N′-dimethylformamidinato)di-trimethylphosphineruthenium (II).  
   
   
       8 . The process of  claim 1  wherein the organometallic compound produced by process (2) comprises tris(N,N′-diisopropylacetamidinato)ruthenium (III), tris(N,N′-diisopropylformamidinato)ruthenium (III), tris(N,N′-di-n-propylacetamidinato)ruthenium (III), tris(N,N′-di-n-propylformamidinato)ruthenium (III), tris(N,N′-diethylacetamidinato)ruthenium (III), tris(N,N′-diethylformamidinato)ruthenium (III), tris(N,N′-dimethylacetamidinato)ruthenium (III), or tris(N,N′-dimethylformamidinato)ruthenium (III).  
   
   
       9 . The process of  claim 1  wherein the solvent is selected from saturated and unsaturated hydrocarbons, aromatic hydrocarbons, aromatic heterocycles, alkyl halides, silylated hydrocarbons, ethers, polyethers, thioethers, esters, thioesters, lactones, amides, amines, polyamines, nitrites, silicone oils, other aprotic solvents, or mixtures of one or more of the above.  
   
   
       10 . An organometallic ruthenium compound represented by the formula  
     
       
         
         
             
             
         
       
       wherein R 1 , R 2 , R 3 , R 4 , R 5  and R 6  are the same or different and each represents hydrogen, a halogen atom, an acyl group having from 1 to about 12 carbon atoms, an alkoxy group having from 1 to about 12 carbon atoms, an alkoxycarbonyl group having from 1 to about 12 carbon atoms, an alkyl group having from 1 to about 12 carbon atoms, an amine group having from 1 to about 12 carbon atoms or a silyl group having from 0 to about 12 carbon atoms, and L 1  and L 2  are the same or different and each represents N 2  or a substituted or unsubstituted heteroatom-containing group.  
     
   
   
       11 . The organometallic ruthenium compound of  claim 10  wherein L 1  and L 2  are the same or different and each represents N 2 , CO, NCR 7 , PR 7 R 8 R 9  or NR 7 R 8 R 9 , wherein R 7 , R 8  and R 9  are the same or different and each represents hydrogen, a halogen atom, an acyl group having from 1 to about 12 carbon atoms, an alkoxy group having from 1 to about 12 carbon atoms, an alkoxycarbonyl group having from 1 to about 12 carbon atoms, an alkyl group having from 1 to about 12 carbon atoms, an amine group having from 1 to about 12 carbon atoms or a silyl group having from 0 to about 12 carbon atoms.  
   
   
       12 . The organometallic ruthenium compound of  claim 10  selected from bis(N,N′-diisopropylacetamidinato)bis(dinitrogen)ruthenium (II), bis(N,N′-diisopropylacetamidinato)dicarbonylruthenium (II), bis(N,N′-diisopropylformamidinato)bis(dinitrogen)ruthenium (II), bis(N,N′-diisopropylformamidinato)di-trimethylphosphineruthenium (II), bis(N,N′-diisopropylformamidinato)dicarbonylruthenium (II), bis(N,N′-di-n-propylacetamidinato)bis(dinitrogen)ruthenium (II), bis(N,N′-di-n-propylacetamidinato)dicarbonylruthenium (II), bis(N,N′-di-n-propylformamidinato)bis(dinitrogen)ruthenium (II), bis(N,N′-di-n-propylformamidinato)di-trimethylphosphineruthenium (II), bis(N,N′-di-n-propylformamidinato)dicarbonylruthenium (II), bis(N,N′-diethylacetamidinato)bis(dinitrogen)ruthenium (II), bis(N,N′-diethylacetamidinato)di-trimethylphosphineruthenium (II), bis(N,N′-diethylformamidinato)bis(dinitrogen)ruthenium (II), bis(N,N′-diethylformamidinato)di-trimethylphosphineruthenium (II), bis(N,N′-dimethylacetamidinato)bis(dinitrogen)ruthenium (II), bis(N,N′-dimethylacetamidinato)di-trimethylphosphineruthenium (II), bis(N,N′-dimethylformamidinato)bis(dinitrogen)ruthenium (II), and bis(N,N′-dimethylformamidinato)di-trimethylphosphineruthenium (II).  
   
   
       13 . The organometallic ruthenium compound of  claim 10  that has undergone hydrogen reduction.  
   
   
       14 . A method for producing a film, coating or powder by decomposing an organometallic ruthenium precursor compound of  claim 10 , thereby producing the film, coating or powder.  
   
   
       15 . The method of  claim 14  wherein the decomposing of said organometallic ruthenium precursor compound is thermal, chemical, photochemical or plasma-activated.  
   
   
       16 . The method of  claim 15  wherein said organometallic ruthenium precursor compound is vaporized and the vapor is directed into a deposition reactor housing a substrate.  
   
   
       17 . The method of  claim 16  wherein said substrate is comprised of a material selected from the. group consisting of a metal, a metal silicide, a semiconductor, an insulator and a barrier material.  
   
   
       18 . The method of  claim 17  wherein said substrate is a patterned wafer.  
   
   
       19 . The method of  claim 14  wherein said film, coating or powder is produced by a gas phase deposition.  
   
   
       20 . The method of  claim 19  wherein said gas phase deposition is self-limiting and is conducted in the presence of a reactive gas.  
   
   
       21 . A mixture comprising (i) a first organometallic ruthenium compound represented by the formula  
     
       
         
         
             
             
         
       
       wherein R 1 , R 2 , R 3 , R 4 , R 5  and R 6  are the same or different and each represents hydrogen, a halogen atom, an acyl group having from 1 to about 12 carbon atoms, an alkoxy group having from 1 to about 12 carbon atoms, an alkoxycarbonyl group having from 1 to about 12 carbon atoms, an alkyl group having from 1 to about 12 carbon atoms, an amine group having from 1 to about 12 carbon atoms or a silyl group having from 0 to about 12 carbon atoms, and L 1  and L 2  are the same or different and each represents N 2  or a substituted or unsubstituted heteroatom-containing group, and (ii) one or more different organometallic compounds.  
     
   
   
       22 . The mixture of  claim 21  wherein said one or more different organometallic compounds are selected from a hafnium-containing, tantalum-containing or molybdenum-containing organometallic compound.