Tantalum amide precursors for deposition of tantalum nitride on a substrate

Claim 1

A method of forming Ta or Ti material on a substrate from a precursor, comprising vaporizing said precursor to form a precursor vapor, and contacting the precursor vapor with the substrate to form said Ta or Ti material thereon, wherein the precursor comprises at least one tantalum and/or titanium species selected from the group consisting of: (i) tethered amine tantalum complexes of the formula: wherein: x is 2 or 3; each of R 1 -R 5 is independently selected from the group consisting of H, C 1 -C 4 alkyl, aryl, C 1 -C 6 perfluoroalkyl and trimethylsilyl; (ii) β-diimines of the formula: TaG x Q 5−x wherein: G is a β-diimino ligand; each Q is selected from the group consisting of H, C 1 -C 6 alkyl, aryl and C 1 -C 6 perfluoroalkyl; and x is an integer from 1 to 4 inclusive; (iii) tantalum diamide complexes of the formula Ta(N(R 1 )(CH 2 ) x N(R 2 )) y (NR 3 R 4 ) 5−2 wherein: x is the integer 1 or 2; y is the integer 1 or 2; each of R 1 -R 4 is independently selected from the group consisting of H, C 1 -C 4 alkyl, aryl, perfluoroalkyl, and trimethylsilyl; (iv) tantalum amide compounds of the formula Ta(NRR′) 5 wherein each R and R′ is independently selected from the group consisting of H, C 1 -C 4 alkyl, phenyl, perfluoroalkyl, and trimethylsilyl, subject to the proviso that in each NRR′ group, R≠R′; (v) β-ketoimines of the formula wherein each of R 1 , R 2 , R a , R b , R c and R d is independently selected from H, aryl, C 1 -C 6 alkyl, and C 1 -C 6 perfluoroalkyl; and (vi) tantalum cyclopentadienyl compounds of the formula wherein each R is trimethylsilyl; (vii) Ta(NR 1 R 2 ) x (NR 3 R 4 ) 5−x /Ti(NR 1 R 2 ) y (NR 3 R 4 ) 4−y wherein each of R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of H, C 1 -C 8 alkyl aryl, C 1 -C 8 perfluoroalkyl or a silicon-containing group selected from the group consisting of silane, alkylsilane, perfluoroalkylsilyl, triarylsilane and alkylsilylsilane, wherein x is an integer from 1 to 5 inclusive; and y is an integer from 1 to 4 inclusive; (viii) Ta(NR 1 )(NR 2 R 3 ) 3 wherein each of R 1 , R 2 , and R 3 are independently selected from the group consisting of H, C 1 -C 8 alkyl aryl, C 1 -C 8 perfluoroalkyl or a silicon-containing group selected from the group consisting of silane, alkylsilane, perfluoroalkylsilyl, triarylsilane and alkylsilylsilane, with the proviso that R 1 ≠C 3 -C 5 alkyl group when R 2 =R 3 =E t (ix) Ta(SiR 1 R 2 R 3 ) x (NR 4 R 5 ) 5−x /Ti(SiR 1 R 2 R 3 ) y (NR 4 R 5 ) 4−y wherein each of R 1-5 is independently selected from the group consisting of H, Me, Et, t Bu, Ph, i Pr, CF 3 , SiH 3 , SiMe 3 , Si(CF 3 ) 3 , Si(Et) 3 , Si( i Pr) 3 , Si( t Bu) 3 , Si(Ph) 3 , and Si(SiMe 3 ) z (Me) 3−z , wherein x is an integer from 1 to 4 inclusive; y is an integer from 1 to 3 inclusive; and z is an integer from 1 to 3 inclusive; and (x) (Cp n )Ta(SiR 1 R 2 R 3 ) x (NR 4 R 5 ) 4−x /(Cp n ) 2 Ti(SiR 1 R 2 R 3 )(NR 4 R 5 ) wherein each of R 1-5 is independently selected from the group consisting of H, Me, Et, t Bu, Ph, i Pr, CF 3 , SiH 3 , SiMe 3 , Si(CF 3 ) 3 , Si(Et) 3 , Si( i Pr) 3 , Si( t Bu) 3 , Si(Ph) 3 , Si(SiMe 3 ) y (Me) 3−y and Cp n is C 5 H z Me (5−z) , wherein x is an integer from 1 to 3 inclusive; y is an integer from 1 to 3 inclusive; and z is an integer from 0 to 5 inclusive.

Claim 2

A method of forming Ta or Ti material on a substrate from a precursor, comprising vaporizing said precursor to form a precursor vapor, and contacting the precursor vapor with the substrate to form said Ta or Ti material thereon, wherein the precursor comprises at least one tantalum and/or titanium species selected from the group consisting of: (i) tethered amine tantalum complexes of the formula: wherein: x is 2 or 3; each of R 1 -R 5 is independently selected from the group consisting of H, C 1 -C 4 alkyl, aryl, C 1 -C 6 perfluoroalkyl and trimethylsilyl; (ii) β-diimines of the formula: TaG x Q 5−x wherein: G is a β-diimino ligand; each Q is selected from the group consisting of H, C 1 -C 6 alkyl, aryl and C 1 -C 6 perfluoroalkyl; and x is an integer from 1 to 4 inclusive; (iii) tantalum diamide complexes of the formula Ta(N(R 1 )(CH 2 ) x N(R 2 )) y (NR 3 R 4 ) 5−2 wherein: x is the integer 1 or 2; y is the integer 1 or 2; each of R 1 -R 4 is independently selected from the group consisting of H, C 1 -C 4 alkyl, aryl, perfluoroalkyl, and trimethylsilyl; (iv) tantalum amide compounds of the formula Ta(NRR′) 5 wherein each R and R′ is independently selected from the group consisting of H, C 1 -C 4 alkyl, phenyl, perfluoroalkyl, and trimethylsilyl, subject to the proviso that in each NRR′ group, R≠R′; (v) β-ketoimines of the formula wherein each of R 1 , R 2 , R a , R b , R c and R d is independently selected from H, aryl, C 1 -C 6 alkyl, and C 1 -C 6 perfluoroalkyl; and (vi) tantalum cyclopentadienyl compounds of the formula wherein each R is trimethylsilyl; (vii) Ta(NR 1 R 2 ) x (NR 3 R 4 ) 5−x /Ti(NR 1 R 2 ) y (NR 3 R 4 ) 4−y wherein each of R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of H, C 1 -C 8 alkyl aryl, C 1 -C 8 perfluoroalkyl or a silicon-containing group selected from the group consisting of silane, alkylsilane, perfluoroalkylsilyl, triarylsilane and alkylsilylsilane, wherein x is an integer from 1 to 5 inclusive; and y is an integer from 1 to 4 inclusive; (viii) Ta(NR 1 )(NR 2 R 3 ) 3 wherein each of R 1 , R 2 , and R 3 are independently selected from the group consisting of H, C 1 -C 8 alkyl aryl, C 1 -C 8 perfluoroalkyl or a silicon-containing group selected from the group consisting of silane, alkylsilane, perfluoroalkylsilyl, triarylsilane and alkylsilylsilane, with the proviso that R 1 ≠C 3 -C 5 alkyl group when R 2 =R 3 =E t (ix) Ta(SiR 1 R 2 R 3 ) x (NR 4 R 5 ) 5−x /Ti(SiR 1 R 2 R 3 ) y (NR 4 R 5 ) 4−y wherein each of R 1-5 is independently selected from the group consisting of H, Me, Et, t Bu, Ph, i Pr, CF 3 , SiH 3 , SiMe 3 , Si(CF 3 ) 3 , Si(Et) 3 , Si( i Pr) 3 , Si( t Bu) 3 , Si(Ph) 3 , and Si(SiMe 3 ) z (Me) 3−z , wherein x is an integer from 1 to 4 inclusive; y is an integer from 1 to 3 inclusive; and z is an integer from 1 to 3 inclusive; and (x) (Cp n )Ta(SiR 1 R 2 R 3 ) x (NR 4 R 5 ) 4−x /(Cp n ) 2 Ti(SiR 1 R 2 R 3 )(NR 4 R 5 ) wherein each of R 1-5 is independently selected from the group consisting of H, Me, Et, t Bu, Ph, i Pr, CF 3 , SiH 3 , SiMe 3 , Si(CF 3 ) 3 , Si(Et) 3 , Si( i Pr) 3 , Si( t Bu) 3 , Si(Ph) 3 , Si(SiMe 3 ) y (Me) 3−y and Cp n is C 5 H z Me (5−z) , wherein x is an integer from 1 to 3 inclusive; y is an integer from 1 to 3 inclusive; and z is an integer from 0 to 5 inclusive.

Claim 14

A method of depositing a tantalum-containing film on a substrate, comprising vaporizing a precursor composition comprising pentakis(N-methyl, N-ethylamido)tantalum to form a precursor vapor, and contacting said vapor with the substrate to deposit said tantalum-containing film on the substrate.

Claim 15

A method of depositing a tantalum-containing film on a substrate, comprising vaporizing a precursor composition comprising pentakis(N-methyl, N-ethylamido)tantalum to form a precursor vapor, and contacting said vapor with the substrate to deposit said tantalum-containing film on the substrate.

Claim 17

A method of fabricating a microelectronic device structure, comprising vaporizing a precursor composition comprising pentakis(N-methyl, N-ethylamido)tantalum to form a precursor vapor, and contacting said vapor with a substrate to deposit a tantalum-containing film on the substrate, and thereafter metallizing the substrate with copper or integrating it with a ferroelectric thin film.

Claim 18

A method of fabricating a microelectronic device structure, comprising vaporizing a precursor composition comprising pentakis(N-methyl, N-ethylamido)tantalum to form a precursor vapor, and contacting said vapor with a substrate to deposit a tantalum-containing film on the substrate, and thereafter metallizing the substrate with copper or integrating it with a ferroelectric thin film.