Methods of forming thin metal-containing films by chemical phase deposition

1. A method of forming a metal-containing thin film by atomic layer deposition, the method comprising delivering at least one precursor to a substrate, wherein the precursor corresponds in structure to Formula II:

Cp(R) n M(CO) 2 (X)  (Formula II)

wherein:

M is Ru or Os;

R is C 1 -C 10 -alkyl;

X is C 1 -C 10 -alkyl;

n is zero, 1, 2, 3, 4 or 5.

2. The method of claim 1 , wherein the at least one precursor corresponds in structure to Formula II wherein:

M is Ru;

R is methyl, ethyl, propyl or butyl;

X is methyl, ethyl, propyl or butyl; and

n is zero, 1 or 2.

3. The method of claim 1 , wherein the at least one precursor corresponds in structure to Formula II wherein:

M is Ru;

R is methyl or ethyl;

X is methyl or ethyl; and

n is zero or 1.

4. The method of claim 1 , wherein the at least one precursor corresponds in structure to Formula II wherein:

M is Os;

R is methyl, ethyl, propyl or butyl;

X is methyl, ethyl, propyl or butyl; and

n is zero, 1 or 2.

5. The method of claim 1 , wherein the at least one precursor corresponds in structure to Formula II wherein:

M is Os;

R is methyl or ethyl;

X is methyl or ethyl; and

n is zero or 1.

6. The method of claim 1 , wherein the at least one precursor corresponding in structure to Formula II is selected from the group consisting of:

(cyclopentadienyl)ruthenium(methyl)(dicarbonyl);

(cyclopentadienyl)ruthenium(ethyl)(dicarbonyl);

(cyclopentadienyl)osmium(methyl)(dicarbonyl);

(cyclopentadienyl)osmium(ethyl)(dicarbonyl);

(methylcyclopentadienyl)ruthenium(methyl)(dicarbonyl);

(ethylcyclopentadienyl)ruthenium(methyl)(dicarbonyl);

(propylcyclopentadienyl)ruthenium(methyl)(dicarbonyl);

(butylcyclopentadienyl)ruthenium(methyl)(dicarbonyl);

(methylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl);

(ethylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl);

(propylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl);

(butylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl);

(methylcyclopentadienyl)osmium(methyl)(dicarbonyl);

(ethylcyclopentadienyl)osmium(methyl)(dicarbonyl);

(propylcyclopentadienyl)osmium(methyl)(dicarbonyl);

(butylcyclopentadienyl)osmium(methyl)(dicarbonyl);

(methylcyclopentadienyl)osmium(ethyl)(dicarbonyl);

(ethylcyclopentadienyl)osmium(ethyl)(dicarbonyl);

(propylcyclopentadienyl)osmium(ethyl)(dicarbonyl); and

(butylcyclopentadienyl)osmium(ethyl)(dicarbonyl).

7. The method of claim 1 , wherein the at least one precursor corresponding in structure to Formula II is selected from the group consisting of:

(cyclopentadienyl)ruthenium(methyl)(dicarbonyl);

(cyclopentadienyl)ruthenium(ethyl)(dicarbonyl);

(cyclopentadienyl)osmium(methyl)(dicarbonyl); and

(cyclopentadienyl)osmium(ethyl)(dicarbonyl).

8. The method of claim 1 , wherein the at least one precursor corresponding in structure to Formula II is (cyclopentadienyl)ruthenium(ethyl)(dicarbonyl).

9. The method of claim 1 , wherein the atomic layer deposition is photo-assisted atomic layer deposition.

10. The method of claim 1 , wherein the atomic layer deposition is liquid injection atomic layer deposition.

11. The method of claim 1 , further comprising delivering at least one appropriate co-reactant selected from the group consisting of hydrogen, hydrogen plasma, oxygen, air, water, ammonia, hydrazine, allylhydrazine, borane, silane, ozone and a combination thereof to the substrate.

12. The method of claim 1 , wherein the at least one precursor is delivered to the substrate in pulses alternating with pulses of an oxygen source.

13. The method of claim 12 , wherein the oxygen source is selected from H 2 O, O 2 or ozone.

14. The method of claim 1 , wherein the metal-containing thin film is used for memory and logic applications.

15. A method of forming a metal-containing thin film by chemical vapor deposition, the method comprising delivering at least one precursor to a substrate, wherein the precursor corresponds in structure to Formula II:

Cp(R) n M(CO) 2 (X)  (Formula II)

wherein:

M is Ru or Os;

R is C 1 -C 10 -alkyl;

X is C 1 -C 10 -alkyl; and

n is 0, 1, 2, 3, 4 or 5.

16. The method of claim 15 , wherein the at least one precursor corresponds in structure to Formula II wherein:

M is Ru;

R is methyl, ethyl, propyl or butyl;

X is methyl, ethyl, propyl or butyl; and

n is zero, 1 or 2.

17. The method of claim 15 , wherein the at least one precursor corresponds in structure to Formula II wherein:

M is Ru;

R is methyl or ethyl;

X is methyl or ethyl; and

n is zero or 1.

18. The method of claim 15 , wherein the at least one precursor corresponds in structure to Formula II wherein:

M is Os;

R is methyl, ethyl, propyl or butyl;

X is methyl, ethyl, propyl or butyl; and

n is zero, 1 or 2.

19. The method of claim 15 , wherein the at least one precursor corresponds in structure to Formula II wherein:

M is Os;

R is methyl or ethyl;

X is methyl or ethyl; and

n is zero or 1.

20. The method of claim 15 , wherein the at least one precursor corresponding in structure to Formula II is selected from the group consisting of:

(cyclopentadienyl)ruthenium(methyl)(dicarbonyl);

(cyclopentadienyl)ruthenium(ethyl)(dicarbonyl);

(cyclopentadienyl)osmium(methyl)(dicarbonyl);

(cyclopentadienyl)osmium(ethyl)(dicarbonyl);

(methylcyclopentadienyl)ruthenium(methyl)(dicarbonyl);

(ethylcyclopentadienyl)ruthenium(methyl)(dicarbonyl);

(propylcyclopentadienyl)ruthenium(methyl)(dicarbonyl);

(butylcyclopentadienyl)ruthenium(methyl)(dicarbonyl);

(methylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl);

(ethylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl);

(propylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl);

(butylcyclopentadienyl)ruthenium(ethyl)(dicarbonyl);

(methylcyclopentadienyl)osmium(methyl)(dicarbonyl);

(ethylcyclopentadienyl)osmium(methyl)(dicarbonyl);

(propylcyclopentadienyl)osmium(methyl)(dicarbonyl);

(butylcyclopentadienyl)osmium(methyl)(dicarbonyl);

(methylcyclopentadienyl)osmium(ethyl)(dicarbonyl);

(ethylcyclopentadienyl)osmium(ethyl)(dicarbonyl);

(propylcyclopentadienyl)osmium(ethyl)(dicarbonyl); and

(butylcyclopentadienyl)osmium(ethyl)(dicarbonyl).

21. The method of claim 15 , wherein the at least one precursor corresponding in structure to Formula II is selected from the group consisting of:

(cyclopentadienyl)ruthenium(methyl)(dicarbonyl);

(cyclopentadienyl)ruthenium(ethyl)(dicarbonyl);

(cyclopentadienyl)osmium(methyl)(dicarbonyl); and

(cyclopentadienyl)osmium(ethyl)(dicarbonyl).

22. The method of claim 15 , wherein the at least one precursor corresponding in structure to Formula II is (cyclopentadienyl)ruthenium(ethyl)(dicarbonyl).

23. The method of claim 15 , wherein the chemical vapor deposition is photo-assisted chemical vapor deposition.

24. The method of claim 15 , wherein the chemical vapor deposition is liquid injection chemical vapor deposition.

25. The method of claim 15 , further comprising delivering at least one appropriate co-reactant selected from the group consisting of hydrogen, hydrogen plasma, oxygen, air, water, ammonia, hydrazine, allylhydrazine, borane, silane, ozone and a combination thereof to the substrate.

26. The method of claim 15 , wherein the at least one precursor is delivered to the substrate in pulses alternating with pulses of an oxygen source.

27. The method of claim 26 , wherein the oxygen source is selected from H 2 O, O 2 or ozone.

28. The method of claim 15 , wherein the metal-containing thin film is used for memory and logic applications.

29. A method of preparing a ruthenium precursor of Formula II,

Cp(R) n M(CO) 2 (X)  (Formula II)

wherein:

M is Ru;

R is C 1 -C 10 -alkyl;

X is C 1 -C 10 -alkyl; and

n is zero, 1, 2, 3, 4 or 5,

the method comprising:

reacting Ru 3 (CO) 12 with 3(CpR n )H to yield 3Ru(CpR n )(CO) 2 H and 6CO;

reacting Ru(CpR n )(CO) 2 H with BuLi to yield Li[Ru(CpR n )(CO) 2 ] and BuH;

and

reacting Li[Ru(CpR n )(CO) 2 ] with XBr to yield Ru(CpR n )(CO) 2 X and LiBr.