Bis(trimethylsilyl) six-membered ring systems and related compounds as reducing agents for forming layers on a substrate
A first compound having an atom in an oxidized state is reacted with a bis(trimethylsilyl) six-membered ring system or related compound to form a second compound having the atom in a reduced state relative to the first compound. The atom in an oxidized state is selected from the group consisting of Groups 2-12 of the Periodic Table, the lanthanides, As, Sb, Bi, Te, Si, Ge, Sn, and Al.
1. A method comprising:
providing a vapor of a first compound having an atom in an oxidized state, the atom in an oxidized state being in an oxidation state greater than 0, the atom in an oxidized state being selected from the group consisting of Groups 2-12 of the Periodic Table, the lanthanides, As, Sb, Bi, Te, Si, Ge, Sn, and Al;
providing a vapor of a reducing agent, the reducing agent selected from the group consisting of compounds described by formulae IA and IB:
wherein:
X 1 is CR 6 (SiR 1 R 1′ R 1″ ) or N(SiR 1 R 1′ R 1″ );
X 2 is CR 7 (SiR 1 R 1′ R 1 ″) or N(SiR 1 R 1′ R 1″ ); and
R 1 , R 1′ , R 1″ , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently H, C 1-10 alkyl, C 6-14 aryl, or C 4-14 heteroaryl; and
reacting the vapor of the first compound with the vapor of the reducing agent to convert the atom to a zero oxidation state.
2. The method of claim 1 wherein R 1 , R 1′ , R 1″ are each independently C 1-10 alkyl; R 2 , R 3 , R 4 , R 5 are each independently H or C 1-10 alkyl; and R 6 and R 7 are H.
3. The method of claim 1 wherein the reducing agent is selected from the group consisting of:
and combinations thereof.
4. The method of claim 3 wherein R 1 , R 1′ , R 1″ are each independently C 1-10 alkyl; R 2 , R 3 , R 4 , R 5 are each independently H or C 1-10 alkyl; and R 6 , and R 7 are H.
5. The method of claim 4 wherein the reducing agent is:
6. The method of claim 1 wherein the atom is in a positive oxidation state of 1, 2, 3, 4, 5, or 6.
7. The method of claim 1 wherein R 2 , R 3 , R 4 , and R 5 are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, or phenyl.
8. The method of claim 1 wherein R 1 , R 1′ , and R 1″ are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, or phenyl.
9. The method of claim 1 wherein the atom is Cu, Cr, Mn, Fe, Co, Ti, or Ni.
10. The method of claim 1 comprising a deposition cycle including:
a) contacting a substrate with the vapor of the first compound having an atom in an oxidized state to form a first modified surface; and
c) contacting the first modified surface with the vapor of the reducing agent.
11. The method of claim 10 wherein a metal-containing layer is deposited on the substrate.
12. The method of claim 11 wherein the metal-containing layer includes a metal atom in the zero oxidation state.
13. The method of claim 10 wherein the reducing agent is described by formula (IIA):
14. The method of claim 10 wherein the substrate is additionally contacted with the vapor of the first compound having an atom in an oxidized state and then the vapor of a reducing agent during a plurality of additional deposition cycles.
15. The method of claim 14 wherein the substrate is coated with from 1 to 5000 deposition cycles.
16. The method of claim 10 wherein the substrate is coated at a temperature from about 50 to 400° C.
17. The method of claim 10 wherein the substrate is contacted with a purge gas after contacting the substrate with vapor of a metal-containing compound including a metal atom in an oxidized state and before contacting the substrate with the vapor of the reducing agent.
18. The method of claim 17 wherein the substrate is contacted with the purge gas after contacting the substrate with the vapor of the reducing agent and before a subsequent step of contacting vapor of a metal-containing compound including a metal atom in an oxidized state.
19. The method of claim 10 wherein the first compound having an atom in an oxidized state is reacted with the reducing agent in a gaseous state.
20. A method of forming a layer on a substrate, the method comprising a deposition cycle including:
a) contacting a substrate with a vapor of a first compound having an atom in an oxidized state to form a first modified surface, the atom in an oxidized state selected from the group consisting of Groups 2-12 of the Periodic Table, the lanthanides, As, Sb, Bi, Te, Si, Ge, Sn, and Al;
b) contacting the first modified surface with an acid for a second predetermined pulse time to form a second modified surface; and
c) contacting the second modified surface with a reducing agent for a third predetermined pulse time to reduce the atom to a zero oxidation state and to form a layer on the substrate, the reducing agent selected from the group consisting of:
wherein:
X 1 is CR 6 (SiR 1 R 1′ R 1″ ) or N(SiR 1 R 1′ R 1″ );
X 2 is CR 7 (SiR 1 R 1′ R 1″ ) or N(SiR 1 R 1′ R 1″ ); and
R 1 , R 1′ , R 1″ , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently H, C 1-10 alkyl, C 6-14 aryl, or C 4-14 heteroaryl.
21. The method of claim 20 wherein the atom is Cu, Cr, Mn, Fe, Co, Ti, or Ni.
22. The method of claim 20 wherein the reducing agent comprises a compound selected from the group consisting of:
and combinations thereof.
23. The method of claim 20 wherein the reducing agent is:
24. The method of claim 20 wherein the atom is in a positive oxidation state of 1, 2, 3, 4, 5, or 6.
25. The method of claim 20 wherein R 1 , R 1′ , R 1″ are each independently C 1-10 alkyl; R 1 , R 2 , R 3 , R 4 , R 5 are each independently H or C 1-10 alkyl; and R 6 , and R 7 are H.
26. The method of claim 20 wherein R 1 , R 1′ , R 1″ are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or t-butyl and R 2 , R 3 , R 4 , and R 5 are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or t-butyl.
27. The method of claim 20 wherein the substrate is additionally contacted with the vapor of the first compound having an atom in an oxidized state, the acid, and the vapor of a reducing agent during a plurality of additional deposition cycles.
28. A method of depositing a thin film on a surface of a substrate, the method comprising:
a) contacting the substrate with a vapor of a metal-containing compound having formula III or IV to form a modified surface on the substrate:
wherein:
M is a transition metal selected from Groups 3-10 of the Periodic Table, Ru, Pd, Pt, Rh, Ir, Mg, Al, Sn, or Sb;
R 8 is C 1 -C 12 alkyl, amino (i.e., —NH 2 ), or C 6 -C 18 aryl;
R 9 is hydrogen, C 1 -C 10 alkyl, C 6 -C 18 aryl, amino, C 1 -C 12 alkylamino, or C 2 -C 22 dialkylamino; and
X is Cl, Br, or I; and
b) contacting the modified surface with a vapor of an activating compound to form a second modified surface, the activating compound being an acid or a diketone; and
c) providing a vapor of a reducing agent to convert M to a zero oxidation state, the reducing agent selected from the group consisting of compounds described by formulae IA and IB:
wherein:
X 1 is CR 6 (SiR 1 R 1′ R 1″ ) or N(SiR 1 R 1′ R 1″ );
X 2 is CR 7 (SiR 1 R 1′ R 1″ ) or N(SiR 1 R 1′ R 1″ );
R 1 , R 1′ , R 1″ , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently H, C 1-10 alkyl, C 6-14 aryl, or C 4-14 heteroaryl.
29. The method of claim 28 wherein steps a) and b) are repeated a plurality of times.
30. The method of claim 29 wherein steps a) and b) are repeated 1 to 5000 times.