Reaction of diazadiene complexes with amines
A method of forming a thin film on a substrate which includes a step of reacting a precursor compound with a Lewis base. The precursor compound has a transition metal and one or more alkyl-1,3-diazabutadiene ligands is provided.
1. A method for depositing a coating on a surface of a substrate, the method comprising:
a) contacting the substrate with a vapor of a metal-containing compound having formula I to form a modified surface on the substrate:
or radicals thereof;
wherein:
M is a transition metal, a group 1 metal, a group 2 metal, Zn, or Cd;
m is an integer;
n is the formal charge of M;
o is an integer such that the overall formal charge of the metal-containing compound having formula I is 0;
p is the formal charge of the ligand within the brackets;
R 1 is C 1-12 alkyl, amine, or C 6-18 aryl; and
R 2 , R 3 are each independently H, C 1-10 alkyl, C 6-18 aryl, amino, C 1-12 alkylamino, or C 2-24 dialkylamino; and
b) contacting the modified surface with a vapor of a Lewis base to form a metal coating on the substrate, the metal coating including metal atoms in the zero-oxidation state, wherein the Lewis base is selected from the group consisting of an alkyl amine, CO, R 7 NC, P(R 8 ) 3 , and P(OR 9 ) 3 , where R 7 , R 8 , and R 9 are each independently H, C 1-6 alkyl or C 6-12 aryl.
2. The method of claim 1 wherein the Lewis base is an alkyl amine.
3. The method of claim 2 wherein the alkyl amine is described by the following formula:
wherein:
R 5 is H or a lower alkyl; and
R 6 is a lower alkyl.
4. The method of claim 1 wherein the Lewis base is selected from the group consisting of methyl amine, ethyl amine, n-propyl amine, isopropyl amine, n-butyl amine, sec-butyl amine, iso-butyl amine, tert-butyl amine, dimethyl amine, diethyl amine, di-n-propyl amine, di-iso-propyl amine, and the like.
5. The method of claim 1 wherein the Lewis base is CO, R 7 NC, P(R 8 ) 3 , or P(OR 9 ) 3 .
6. The method of claim 1 wherein the metal-containing compound having formula I is thermally activated.
7. The method of claim 1 wherein the metal-containing compound having formula I is plasma activated.
8. The method of claim 1 wherein R 2 , R 3 are each independently H or C 1-4 alkyl.
9. The method of claim 1 wherein R 2 , R 3 are each independently H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl.
10. The method of claim 1 wherein R 1 is tert-butyl or isopropyl.
11. The method of claim 1 wherein
n is 0, 1, 2, or 3;
m is 1; and
o is 1, 2, or 3.
12. The method of claim 1 wherein molecular hydrogen is combined with the Lewis base prior to contacting the modified surface.
13. The method of claim 1 wherein M is Cu, Ni, Co, Cr, Mn, Fe, W, Mo, Ti, Zr, Hf, Rf, V, Nb, Ta, Re, Ru, Rh, Ir, Pd, Pt, Au, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Zn, or Cd.
14. The method of claim 1 wherein M is Cr(II), Mn(II), Fe(II), Co(II), or Ni(II).
15. The method of claim 1 wherein the metal-containing compound is described by formulae III:
16. The method of claim 1 wherein the metal-containing compound is described by formulae IV:
17. The method of claim 1 wherein R 1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl.
18. A method comprising:
a) reacting a vapor of a metal-containing compound with a Lewis base to form a metal coating on a substrate, the metal coating including metal atoms in the zero-oxidation state, wherein the Lewis base is selected from the group consisting of an alkyl amine, CO, R 7 NC, P(R 8 ) 3 , and P(OR 9 ) 3 , where R 7 , R 8 , and R 9 are each independently H, C 1-6 alkyl or C 6-12 aryl,
the metal-containing compound being described by formulae I:
or radicals thereof;
wherein:
M is a transition metal, a group 1 metal, a group 2 metal, Zn, or Cd;
m is an integer;
n is the formal charge of M;
o is an integer such that the overall formal charge of the metal-containing compound having formula I is 0;
p is the formal charge of the ligand within the brackets;
R 1 is C 1-12 alkyl, amine, or C 6-18 aryl; and
R 2 , R 3 are each independently H, C 1-10 alkyl, C 6-18 aryl, amino, C 1-12 alkylamino, or C 2-24 or dialkylamino.
19. The method of claim 18 wherein the Lewis base is an alkyl amine.
20. The method of claim 19 wherein the alkyl amine is described by the following formula:
wherein:
R 5 is H or a lower alkyl; and
R 6 is a lower alkyl.
21. The method of claim 18 wherein the Lewis base is selected from the group consisting of methyl amine, ethyl amine, n-propyl amine, isopropyl amine, n-butyl amine, sec-butyl amine, iso-butyl amine, tert-butyl amine, dimethyl amine, diethyl amine, di-n-propyl amine, di-iso-propyl amine, and the like.
22. The method of claim 18 wherein the Lewis base is CO, R 7 NC, P(R 8 ) 3 , or P(OR 9 ) 3 .
23. The method of claim 18 wherein R 2 , R 3 are each independently H or C 1-4 alkyl.
24. The method of claim 18 wherein R 2 , R 3 are each independently H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl.
25. The method of claim 18 wherein R 1 is tert-butyl or isopropyl.
26. The method of claim 18 wherein
n is 0, 1, 2, or 3;
m is 1; and
o is 1, 2, or 3.
27. The method of claim 18 wherein molecular hydrogen is combined with the Lewis base and the metal-containing compound having formula 1.
28. The method of claim 18 wherein M is Cu, Ni, Co, Cr, Mn, Fe, W, Mo, Ti, Zr, Hf, Rf, V, Nb, Ta, Re, Ru, Rh, Ir, Pd, Pt, Au, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Zn, or Cd.
29. The method of claim 18 wherein M is Cr(II), Mn(II), Fe(II), Co(II), or Ni(II).
30. The method of claim 18 wherein the metal-containing compound is described by formulae II:
31. The method of claim 18 wherein the metal-containing compound is described by formulae IV:
32. The method of claim 18 wherein R 1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl.