Formulation for deposition of silicon doped hafnium oxide as ferroelectric materials

1. An Atomic Layer Deposition or a Plasma Enhanced Atomic Layer Deposition composition for depositing a silicon doped hafnium oxide film comprising:

1) at least one organoaminosilane precursor compound having a formula of R x R 3 Si(NR 1 R 2 ) 3-x ;

wherein

R is a linear or branched C 1 to C 6 alkyl;

R 1 , R 2 and R 3 are independently selected from linear or branched C 1 to C 6 alkyl; wherein

R 1 and R 2 in organoamino group are linked to form a cyclic ring structure; or not linked to form a cyclic ring structure; and

x=0, 1, or 2;

and

(b) at least one organoaminohafnium precursor compound having a formula of

L x Hf(NR 1 R 2 ) 4-x ;

wherein

L is cyclopentadienyl or alkyl substituted cyclopentadienyl;

R 1 and R 2 are independently selected from linear or branched C 1 to C 6 alkyl in organoamino group; wherein

R 1 and R 2 are linked to form a cyclic ring structure or R 1 and R 2 are not linked to form a cyclic ring structure; and

x=0, 1, or 2;

wherein melting point of the composition is ≤30° C.; and

the at least one organoaminosilane precursor and the at least one organoaminohafnium precursor have the same organoamino group.

2. The composition of claim 1 , wherein the at least one organoaminosilane precursor compound is selected from the group consisting of tris(dimethylamino)methylsilane, tris(diethylamino)methylsilane, tris(ethylmethylamino)methylsilane, tris(pyrrolidino)methylsilane, tris(dimethylamino)ethylsilane, tris(diethylamino)ethylsilane, tris(ethylmethylamino)ethylsilane, tris(pyrrolidino)ethylsilane, bis(dimethylamino)dimethylsilane, bis(diethylamino)dimethylsilane, bis(ethylmethylamino)dimethylsilane, bis(pyrrolidino)dimethylsilane, bis(dimethylamino)diethylsilane, bis(diethylamino)diethylsilane, bis(ethylmethylamino)diethylsilane, bis(pyrrolidino)diethylsilane, dimethylaminotrimethylsilane, diethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, pyrrolidinotrimethylsilane, dimethylaminotriethylsilane, diethylaminotriethylsilane, ethylmethylaminotriethylsilane, pyrrolidinotriethylsilane, dimethylaminophenyldimethylsilane, diethylaminophenyldimethylsilane, ethylmethylaminophenyldimethylsilane, pyrrolidinophenyldimethylsilane, tris(dimethylamino)phenylsilane, tris(diethylamino)phenylsilane, tris(ethylmethylamino)phenylsilane, tris(pyrrolidino)phenylsilane, 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1,1,1,4,4,4-hexakis(dimethylamino)-1,4-disilabutane, 2,5-bis(dimethylamino)-2,5-dimethyl-2,5-disilahexane and combinations thereof; and

the at least one organoaminohafnium precursor compound is selected from the group consisting of tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(pyrrolidino)hafnium, cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe 2 ) 3 ), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMe 2 ) 3 ), ethylcyclopentadienyltris(dimethylamino)hafnium (EtCpHf(NMe 2 ) 3 ), cyclopentadienyltris(ethylmethylamino)hafnium (CpHf(NMeEt) 3 ), methylcyclopentadienyltris(ethylmethylamino)hafnium (MeCpHf(NMeEt) 3 ), ethylcyclopentadienyltris(ethylmethylamino)hafnium (EtCpHf(NMeEt) 3 ), cyclopentadienyltris(diethylamino)hafnium (CpHf(NEt 2 ) 3 ), methylcyclopentadienyltris(diethylamino)hafnium (MeCpHf(NEt 2 ) 3 ), ethylcyclopentadienyltris(diethylamino)hafnium (EtCpHf(NEt 2 ) 3 ), bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp 2 Hf(NMe 2 ) 2 ), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp) 2 Hf(NMe 2 ) 2 ), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp) 2 Hf(NMe 2 ) 2 ), bis(cyclopentadienyl)bis(ethylmethylamino)hafnium (Cp 2 Hf(NMeEt) 2 ), bis(methylcyclopentadienyl)bis(ethylmethylamino)hafnium ((MeCp) 2 Hf(NMeEt) 2 ), bis(ethylcyclopentadienyl)bis(ethylmethylamino)hafnium ((EtCp) 2 Hf(NMeEt) 2 ), bis(cyclopentadienyl)bis(diethylamino)hafnium ((Cp 2 Hf(NEt 2 ) 2 ), bis(methylcyclopentadienyl)bis(diethylamino)hafnium ((MeCp) 2 Hf(NEt 2 ) 3 ), bis(ethylcyclopentadienyl)bis(diethylamino)hafnium ((EtCp) 2 Hf(NEt 2 ) 2 ), (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(dimethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethanamino] bis(dimethylamino)hafnium, (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(diethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene, 1-ethanamino]bis(diethylamino)hafnium, (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(ethylmethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethanamino] bis(ethylmethylamino)hafnium, and combinations thereof.

3. The composition of claim 1 , wherein the at least one organoaminosilane precursor compound is bis(dimethylamino)dimethylsilane; and the at least one organoaminohafnium precursor compound is tetrakis(dimethylamino)hafnium.

4. The composition of claim 1 , wherein the at least one organoaminosilane precursor compound has a range selected from the group consisting of 0.10 to 99.90 wt. %, 0.10 to 30.00 wt. %, 0.10 to 20.00 wt. %, 0.10 to 10.00 wt. %, 5.00 to 30.00 wt. %, 5.00 to 20.00 wt. %, 5.00 to 10.00 wt. %, and 0.10 to 5.00 wt. %; and the at least one organoaminohafnium precursor compound has a range selected from the group consisting of 0.10 to 99.00 wt. %, 0.10 to 30.00 wt. %, 0.10 to 20.00 wt. %, 0.10 to 10.00 wt. %, 5.00 to 30.00 wt. %, 5.00 to 20.00 wt. %, 5.00 to 10.00 wt. %, and 0.10 to 5.00 wt. %.

5. The composition of claim 1 further comprises (c) a solvent selected from the group consisting of ether, tertiary amine, alkyl hydrocarbon, aromatic hydrocarbon, siloxanes, tertiary aminoether, and combinations thereof; the at least one organoaminosilane precursor compound has a range selected from the group consisting of 0.10 to 99.90 wt. %, 10.00 to 90.00 wt. %, 20.00 to 80.00 wt. %, 30.00 to 70.00 wt. %,and 40.00 to 60.00 wt. %; and the at least one organoaminohafnium precursor compound has a range selected from the group consisting of 0.10 to 99.00 wt. %, 10.00 to 90.00 wt. %, 20.00 to 80.00 wt. %, 30.00 to 70.00 wt. %, and 40.00 to 60.00 wt. %.

6. A system to deposit a film comprising silicon, hafnium and oxygen onto a substrate, comprising:

the substrate in a reactor; and

an Atomic Layer Deposition or a Plasma Enhanced Atomic Layer Deposition composition comprising:

(i) at least one organoaminosilane precursor compound having a formula of

R x R 3 Si(NR 1 R 2 ) 3-x ;

wherein

R is a linear or branched Ci to C6 alkyl;

R 1 , R 2 and R 3 are independently selected from linear or branched C 1 to C 6 alkyl; wherein

R 1 and R 2 in organoamino group are linked to form a cyclic ring structure; or not linked to form a cyclic ring structure; and

x=0, 1, or 2;

and

(ii) at least one organoaminohafnium precursor compound having a formula of

L x Hf(NR 1 R 2 ) 4-x ;

wherein

L is cyclopentadienyl or alkyl substituted cyclopentadienyl;

R 1 and R 2 are independently selected from linear or branched C 1 to C 6 alkyl in organoamino group; wherein

R 1 and R 2 are linked to form a cyclic ring structure or R 1 and R 2 are not linked to form a cyclic ring structure; and

x=0, 1, or 2;

wherein

a melting point of the composition is ≤30° C.;

the at least one organoaminosilane precursor and the at least one organoaminohafnium precursor have the same organoamino group; and

the system is at a temperature ranging from 100° C. to 350° C.

7. The system of claim 6 , wherein the composition comprises the at least one organoaminosilane precursor compound is selected from the group consisting of tris(dimethylamino)methylsilane, tris(diethylamino)methylsilane, tris(ethylmethylamino)methylsilane, tris(pyrrolidino)methylsilane, tris(dimethylamino)ethylsilane, tris(diethylamino)ethylsilane, tris(ethylmethylamino)ethylsilane, tris(pyrrolidino)ethylsilane, bis(dimethylamino)dimethylsilane, bis(diethylamino)dimethylsilane, bis(ethylmethylamino)dimethylsilane, bis(pyrrolidino)dimethylsilane, bis(dimethylamino)diethylsilane, bis(diethylamino)diethylsilane, bis(ethylmethylamino)diethylsilane, bis(pyrrolidino)diethylsilane, dimethylaminotrimethylsilane, diethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, pyrrolidinotrimethylsilane, dimethylaminotriethylsilane, diethylaminotriethylsilane, ethylmethylaminotriethylsilane, pyrrolidinotriethylsilane, dimethylaminophenyldimethylsilane, diethylaminophenyldimethylsilane, ethylmethylaminophenyldimethylsilane, pyrrolidinophenyldimethylsilane, tris(dimethylamino)phenylsilane, tris(diethylamino)phenylsilane, tris(ethylmethylamino)phenylsilane, tris(pyrrolidino)phenylsilane, 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1,1,1,4,4,4-hexakis(dimethylamino)-1,4-disilabutane, 2,5-bis(dimethylamino)-2,5-dimethyl-2,5-disilahexane and combinations thereof;

and

the at least one organoaminohafnium precursor compound is selected from the group consisting of tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(pyrrolidino)hafnium, cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe 2 ) 3 ), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMe 2 ) 3 ), ethylcyclopentadienyltris(dimethylamino)hafnium (EtCpHf(NMe 2 ) 3 ), cyclopentadienyltris(ethylmethylamino)hafnium (CpHf(NMeEt) 3 ), methylcyclopentadienyltris(ethylmethylamino)hafnium (MeCpHf(NMeEt) 3 ), ethylcyclopentadienyltris(ethylmethylamino)hafnium (EtCpHf(NMeEt) 3 ), cyclopentadienyltris(diethylamino)hafnium (CpHf(NEt 2 ) 3 ), methylcyclopentadienyltris(diethylamino)hafnium (MeCpHf(NEt 2 ) 3 ), ethylcyclopentadienyltris(diethylamino)hafnium (EtCpHf(NEt 2 ) 3 ), bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp 2 Hf(NMe 2 ) 2 ), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp) 2 Hf(NMe 2 ) 2 ), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp) 2 Hf(NMe 2 ) 2 ), bis(cyclopentadienyl)bis(ethylmethylamino)hafnium (Cp 2 Hf(NMeEt) 2 ), bis(methylcyclopentadienyl)bis(ethylmethylamino)hafnium ((MeCp) 2 Hf(NMeEt) 2 ), bis(ethylcyclopentadienyl)bis(ethylmethylamino)hafnium ((EtCp) 2 Hf(NMeEt) 2 ), bis(cyclopentadienyl)bis(diethylamino)hafnium ((Cp 2 Hf(NEt 2 ) 2 ), bis(methylcyclopentadienyl)bis(diethylamino)hafnium ((MeCp) 2 Hf(NEt 2 ) 3 ), bis(ethylcyclopentadienyl)bis(diethylamino)hafnium ((EtCp) 2 Hf(NEt 2 ) 2 ), (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(dimethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethanamino]bis(dimethylamino)hafnium, (N-methyl-2,4-cyclopentadiene-1-ethanamino] bis(diethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene,1-ethanamino]bis(diethylamino) hafnium, (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(ethylmethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethanamino]bis(ethylmethylamino)hafnium, and combinations thereof.

8. The system of claim 6 , wherein the composition comprises bis(dimethylamino)dimethylsilane; and tetrakis(dimethylamino)hafnium.

9. The system of claim 6 , wherein the composition further comprises (iii) a solvent selected from the group consisting of ether, tertiary amine, alkyl hydrocarbon, aromatic hydrocarbon, siloxanes, tertiary aminoether, and combinations thereof.

10. A silicon doped hafnium oxide film suitable as ferroelectric materials deposited by using an Atomic Layer Deposition or a Plasma Enhanced Atomic Layer Deposition composition comprising

(1) at least one organoaminosilane precursor compound having a formula of

R x R 3 Si(NR 1 R 2 ) 3-x ;

wherein

R is a linear or branched C 1 to C 6 alkyl;

R 1 , R 2 and R 3 are independently selected from linear or branched C 1 to C 6 alkyl; wherein

R 1 and R 2 in organoamino group are linked to form a cyclic ring structure; or not linked to form a cyclic ring structure; and

x=0, 1, or 2;

and

(2) at least one organoaminohafnium precursor compound having a formula of

L x Hf(NR 1 R 2 ) 4-x ;

wherein

L is cyclopentadienyl or alkyl substituted cyclopentadienyl;

R 1 and R 2 are independently selected from linear or branched C 1 to C 6 alkyl; wherein

R 1 and R 2 are linked to form a cyclic ring structure or R 1 and R 2 are not linked to form a cyclic ring structure; and

x=0, 1, or 2;

and

wherein

a melting point of the composition is ≤30° C.;

the at least one organoaminosilane precursor and the at least one organoaminohafnium precursor have the same organoamino group;

deposition process is selected from the group consisting of a thermal atomic layer deposition (ALD), plasma enhanced atomic layer deposition (PEALD) process, and combination thereof; and

the silicon doped hafnium oxide film having a silicon doping level ranging from 2.00 to 6.00 mol %.

11. The silicon doped hafnium oxide film of claim 10 , wherein the at least one organoaminosilane precursor compound is selected from the group consisting of tris(dimethylamino)methylsilane, tris(diethylamino)methylsilane, tris(ethylmethylamino)methylsilane, tris(pyrrolidino)methylsilane, tris(dimethylamino)ethylsilane, tris(diethylamino)ethylsilane, tris(ethylmethylamino)ethylsilane, tris(pyrrolidino)ethylsilane, bis(dimethylamino)dimethylsilane, bis(diethylamino)dimethylsilane, bis(ethylmethylamino)dimethylsilane, bis(pyrrolidino)dimethylsilane, bis(dimethylamino)diethylsilane, bis(diethylamino)diethylsilane, bis(ethylmethylamino)diethylsilane, bis(pyrrolidino)diethylsilane, dimethylaminotrimethylsilane, diethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, pyrrolidinotrimethylsilane, dimethylaminotriethylsilane, diethylaminotriethylsilane, ethylmethylaminotriethylsilane, pyrrolidinotriethylsilane, dimethylaminophenyldimethylsilane, diethylaminophenyldimethylsilane, ethylmethylaminophenyldimethylsilane, pyrrolidinophenyldimethylsilane, tris(dimethylamino)phenylsilane, tris(diethylamino)phenylsilane, tris(ethylmethylamino)phenylsilane, tris(pyrrolidino)phenylsilane, 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1,1,1,4,4,4-hexakis(dimethylamino)-1,4-disilabutane, 2,5-bis(dimethylamino)-2,5-dimethyl-2,5-disilahexane and combinations thereof;

and

the at least one organoaminohafnium precursor compound is selected from the group consisting of tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(pyrrolidino)hafnium, cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe 2 ) 3 ), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMe 2 ) 3 ), ethylcyclopentadienyltris(dimethylamino)hafnium (EtCpHf(NMe 2 ) 3 ), cyclopentadienyltris(ethylmethylamino)hafnium (CpHf(NMeEt) 3 ), methylcyclopentadienyltris(ethylmethylamino)hafnium (MeCpHf(NMeEt) 3 ), ethylcyclopentadienyltris(ethylmethylamino)hafnium (EtCpHf(NMeEt) 3 ), cyclopentadienyltris(diethylamino)hafnium (CpHf(NEt 2 ) 3 ), methylcyclopentadienyltris(diethylamino)hafnium (MeCpHf(NEt 2 ) 3 ), ethylcyclopentadienyltris(diethylamino)hafnium (EtCpHf(NEt 2 ) 3 ), bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp 2 Hf(NMe 2 ) 2 ), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp) 2 Hf(NMe 2 ) 2 ), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp) 2 Hf(NMe 2 ) 2 ), bis(cyclopentadienyl)bis(ethylmethylamino)hafnium (Cp 2 Hf(NMeEt) 2 ), bis(methylcyclopentadienyl)bis(ethylmethylamino)hafnium ((MeCp) 2 Hf(NMeEt) 2 ), bis(ethylcyclopentadienyl)bis(ethylmethylamino)hafnium ((EtCp) 2 Hf(NMeEt) 2 ), bis(cyclopentadienyl)bis(diethylamino)hafnium ((Cp 2 Hf(NEt 2 ) 2 ), bis(methylcyclopentadienyl)bis(diethylamino)hafnium ((MeCp) 2 Hf(NEt 2 ) 3 ), bis(ethylcyclopentadienyl)bis(diethylamino)hafnium ((EtCp) 2 Hf(NEt 2 ) 2 ), (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(dimethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethanamino]bis(dimethylamino)hafnium, (N-methyl-2,4-cyclopentadiene-1-ethanamino] bis(diethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene,1-ethanamino]bis(diethylamino) hafnium, (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(ethylmethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethanamino]bis(ethylmethylamino)hafnium, and combinations thereof.

12. The silicon doped hafnium oxide film of claim 10 , wherein the composition comprises bis(dimethylamino)dimethylsilane; and tetrakis(dimethylamino)hafnium.

13. The silicon doped hafnium oxide film of claim 10 , wherein the composition further comprises (3) a solvent selected from the group consisting of ether, tertiary amine, alkyl hydrocarbon, aromatic hydrocarbon, siloxanes, tertiary aminoether, and combinations thereof.

14. A vessel employing an Atomic Layer Deposition or a Plasma Enhanced Atomic Layer Deposition composition comprising

(1) at least one organoaminosilane precursor compound having a formula of

R x R 3 Si(NR 1 R 2 ) 3-x ;

wherein

R is a linear or branched C 1 to C 6 alkyl;

R 1 , R 2 and R 3 are independently selected from linear or branched C 1 to C 6 alkyl; wherein

R 1 and R 2 in organoamino group are linked to form a cyclic ring structure; or not linked to form a cyclic ring structure;

x=0, 1, or 2; and

(2) at least one organoaminohafnium precursor compound having a formula of

L x Hf(NR 1 R 2 ) 4-x ;

wherein

L is cyclopentadienyl or alkyl substituted cyclopentadienyl;

R 1 and R 2 are independently selected from linear or branched C 1 to C 6 alkyl in organoamino group; wherein

R 1 and R 2 are linked to form a cyclic ring structure or R 1 and R 2 are not linked to form a cyclic ring structure; and

x=0, 1, or 2; wherein

a melting point of the composition is ≤30° C.;

the at least one organoaminosilane precursor and the at least one organoaminohafnium precursor have the same organoamino group; and

the vessel is a pressurizable vessel comprising valves and fittings to allow the delivery of the composition to a reactor fora deposition process selected from the group consisting of a thermal atomic layer deposition (ALD), plasma enhanced atomic layer deposition (PEALD) process, and combination thereof.

15. The vessel of claim 14 , wherein the at least one organoaminosilane precursor compound is selected from the group consisting of tris(dimethylamino)methylsilane, tris(diethylamino)methylsilane, tris(ethylmethylamino)methylsilane, tris(pyrrolidino)methylsilane, tris(dimethylamino)ethylsilane, tris(diethylamino)ethylsilane, tris(ethylmethylamino)ethylsilane, tris(pyrrolidino)ethylsilane, bis(dimethylamino)dimethylsilane, bis(diethylamino)dimethylsilane, bis(ethylmethylamino)dimethylsilane, bis(pyrrolidino)dimethylsilane, bis(dimethylamino)diethylsilane, bis(diethylamino)diethylsilane, bis(ethylmethylamino)diethylsilane, bis(pyrrolidino)diethylsilane, dimethylaminotrimethylsilane, diethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, pyrrolidinotrimethylsilane, dimethylaminotriethylsilane, diethylaminotriethylsilane, ethylmethylaminotriethylsilane, pyrrolidinotriethylsilane, dimethylaminophenyldimethylsilane, diethylaminophenyldimethylsilane, ethylmethylaminophenyldimethylsilane, pyrrolidinophenyldimethylsilane, tris(dimethylamino)phenylsilane, tris(diethylamino)phenylsilane, tris(ethylmethylamino)phenylsilane, tris(pyrrolidino)phenylsilane, 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1,1,1,4,4,4-hexakis(dimethylamino)-1,4-disilabutane, 2,5-bis(dimethylamino)-2,5-dimethyl-2,5-disilahexane and combinations thereof;

and

the at least one organoaminohafnium precursor compound is selected from the group consisting of tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(pyrrolidino)hafnium, cyclopentadienyltris(dimethylamino)hafnium (CpHf(NMe 2 ) 3 ), methylcyclopentadienyltris(dimethylamino)hafnium (MeCpHf(NMe 2 ) 3 ), ethylcyclopentadienyltris(dimethylamino)hafnium (EtCpHf(NMe 2 ) 3 ), cyclopentadienyltris(ethylmethylamino)hafnium (CpHf(NMeEt) 3 ), methylcyclopentadienyltris(ethylmethylamino)hafnium (MeCpHf(NMeEt) 3 ), ethylcyclopentadienyltris(ethylmethylamino)hafnium (EtCpHf(NMeEt) 3 ), cyclopentadienyltris(diethylamino)hafnium (CpHf(NEt 2 ) 3 ), methylcyclopentadienyltris(diethylamino)hafnium (MeCpHf(NEt 2 ) 3 ), ethylcyclopentadienyltris(diethylamino)hafnium (EtCpHf(NEt 2 ) 3 ), bis(cyclopentadienyl)bis(dimethylamino)hafnium (Cp 2 Hf(NMe 2 ) 2 ), bis(methylcyclopentadienyl)bis(dimethylamino)hafnium ((MeCp) 2 Hf(NMe 2 ) 2 ), bis(ethylcyclopentadienyl)bis(dimethylamino)hafnium ((EtCp) 2 Hf(NMe 2 ) 2 ), bis(cyclopentadienyl)bis(ethylmethylamino)hafnium (Cp 2 Hf(NMeEt) 2 ), bis(methylcyclopentadienyl)bis(ethylmethylamino)hafnium ((MeCp) 2 Hf(NMeEt) 2 ), bis(ethylcyclopentadienyl)bis(ethylmethylamino)hafnium ((EtCp) 2 Hf(NMeEt) 2 ), bis(cyclopentadienyl)bis(diethylamino)hafnium ((Cp 2 Hf(NEt 2 ) 2 ), bis(methylcyclopentadienyl)bis(diethylamino)hafnium ((MeCp) 2 Hf(NEt 2 ) 3 ), bis(ethylcyclopentadienyl)bis(diethylamino)hafnium ((EtCp) 2 Hf(NEt 2 ) 2 ), (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(dimethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethanamino]bis(dimethylamino)hafnium, (N-methyl-2,4-cyclopentadiene-1-ethanamino] bis(diethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene,1-ethanamino]bis(diethylamino) hafnium, (N-methyl-2,4-cyclopentadiene-1-ethanamino]bis(ethylmethylamino)hafnium, (N-ethyl-2,4-cyclopentadiene-1-ethanamino]bis(ethylmethylamino)hafnium, and combinations thereof.

16. The vessel of claim 14 , wherein the composition comprises bis(dimethylamino)dimethylsilane; and tetrakis(dimethylamino)hafnium.

17. The vessel of claim 14 , wherein the composition further comprises a solvent selected from the group consisting of ether, tertiary amine, alkyl hydrocarbon, aromatic hydrocarbon, siloxanes, tertiary aminoether, and combinations thereof.

18. The vessel of claim 14 , wherein the composition further comprises an inert gas selected from the group consisting of nitrogen, helium, and argon, and combinations thereof.