Precursor compositions and methods

Abstract

Compositions including an amido-group-containing vapor deposition precursor and a stabilizing additive are provided. Such compositions have improved thermal stability and increased volatility as compared to the amido-group-containing vapor deposition precursor itself. These compositions are useful in the deposition of thin films, such as by atomic layer deposition.

1 . (canceled) 
     
     
         2 . The method of  claim 10  wherein the vapor deposition precursor has the formula (amido) n M +m L 1   (m-n) L 2   p  wherein M=a transition metal, phosphorus, antimony or arsenic; L 1 =an anionic ligand; L 2 =a neutral ligand; m=the valence of M; n=1-6; p=0-3; and m is greater than or equal to n; amido=amidinato, formaminato, haloamidinato, phosphoamidinato, guanidinato, phosphoguanidinato, and (R 1 )NR 2  wherein R 1  and R 2  are independently chosen from H, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 3 -C 8 )cycloalkyl, dialkylaminoalkyl, monoalkylamino, dialkylamino, di(silyl-alkyl)amino, di(alkyl-silyl)amino, disilylamino, alkylalkoxy, alkoxyalkyl and aryl, wherein L 1  is not amido. 
     
     
         3 . The method of  claim 10  wherein the stabilizing additive compound is chosen from amidines, formamidines, haloamidines, phosphoamidines, guanidines, phosphoguanidines, beta-diketones, beta-diketoiminates, alcohols, amines, polyamines, carbodiimides, alkyl carbodiimides, cyclopentadienes, and mixtures thereof. 
     
     
         4 . The method of  claim 10  wherein the stabilizing additive compound comprises an atom chosen from nitrogen, phosphorus, oxygen and sulfur. 
     
     
         5 . The method of  claim 10  wherein the stabilizing additive compound is present in an amount of 0.01 to 2 equivalents based on the vapor deposition precursor. 
     
     
         6 . The method of  claim 10  wherein the stabilizing additive compound is different from any ligands present in the vapor deposition precursor. 
     
     
         7 - 9 . (canceled) 
     
     
         10 . A method of depositing a thin film comprising providing a substrate in a vapor deposition reactor; conveying as a first precursor a composition comprising an amido-group-containing vapor deposition precursor comprising a metal or metalloid chosen from a transition metal, phosphorus, antimony and arsenic, and a stabilizing additive compound capable of sharing electrons with the metal or metalloid, wherein the stabilizing additive compound is present in an amount of 0.01 to 3 molar equivalent based on the vapor deposition precursor; chemisorbing the amido-group-containing vapor deposition precursor on the surface of the substrate; removing any non-chemisorbed amido-group-containing vapor deposition precursor from the reactor; conveying a second precursor in a gaseous form to the reactor; reacting the first and second precursors to form a film on the substrate; and removing any unreacted second precursor. 
     
     
         11 . The method of  claim 2  wherein L 1  is chosen from hydride, halide, azide, alkyls, alkenyl, alkynyl, amino, alkylamino, dialkylamino, di(silyl-alkyl)amino, disilylamino, di(alkyl-silyl)amino, dialkylaminoalkyl, hydrazido, phosphido, nitrile, alkoxy, dialkylaminoalkoxy, alkoxyalkyldialkylamino, siloxy, diketonates, cyclopentadienyls, silyls, beta-diketonato, beta-diiminato, beta-ketoiminato, and pyrazolates. 
     
     
         12 . The method of  claim 11  wherein L 1  is chosen from hydride, azide, alkyls, alkenyl, alkynyl, amino, alkylamino, dialkylamino, di(silyl-alkyl)amino, disilylamino, di(alkyl-silyl)amino, dialkylaminoalkyl, hydrazido, phosphido, nitrile, alkoxy, dialkylaminoalkoxy, alkoxyalkyldialkylamino, siloxy, diketonates, cyclopentadienyls, silyls, beta-diketonato, beta-diiminato, beta-ketoiminato, and pyrazolates. 
     
     
         13 . The method of  claim 3  wherein the stabilizing additive compound is chosen from amidines, formamidines, haloamidines, phosphoamidines, guanidines, phosphoguanidines, beta-diketones, beta-diketoiminates, polyamines, carbodiimides, alkyl carbodiimides, cyclopentadienes, and mixtures thereof. 
     
     
         14 . The method of  claim 10  wherein the second precursor is chosen from oxygen, ozone, water, peroxide, alcohols, nitrous oxide and ammonia.