Methods of atomic layer deposition using hafnium and zirconium-based precursors

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

wherein:

M is Hf or Zr;

R is C 1 -C 6 -alkyl;

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

L is C 1 -C 6 -alkoxy.

2. The method of claim 1 , wherein

M is Hf

R is methyl, ethyl or propyl;

n is zero, 1 or 2; and

L is selected from the group consisting of methoxy, ethoxy, propoxy and butoxy.

3. The method of claim 1 , wherein

M is Hf

R is methyl or ethyl;

n is 1 or 2; and

L is selected from the group consisting of methoxy, ethoxy, propoxy and butoxy.

4. The method of claim 1 , wherein

M is Hf

R is methyl or ethyl;

n is 1; and

L is selected from the group consisting of methoxy, ethoxy, propoxy, and butoxy.

5. The method of claim 1 , wherein

M is Zr;

R is methyl, ethyl or propyl;

n is zero, 1 or 2; and

L is selected from the group consisting of methoxy, ethoxy, propoxy and butoxy.

6. The method of claim 1 , wherein

M is Zr;

R is methyl or ethyl;

n is 1 or 2; and

L is selected from the group consisting of methoxy, ethoxy, propoxy and butoxy.

7. The method of claim 1 , wherein

M is Zr;

R is methyl or ethyl;

n is 1; and

L is selected from the group consisting of methoxy, ethoxy, propoxy and butoxy.

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

(methylcyclopentadienyl)Hf(OMe) 3 ;

(ethylcyclopentadienyl)Hf(OMe) 3 ;

(propylcyclopentadienyl)Hf(OMe) 3 ;

(methylcyclopentadienyl)Hf(OEt) 3 ;

(ethylcyclopentadienyl)Hf(OEt) 3 ;

(propylcyclopentadienyl)Hf(OEt) 3 ;

(methylcyclopentadienyl)Hf(OiPr) 3 ;

(ethylcyclopentadienyl)Hf(OiPr) 3 ;

(propylcyclopentadienyl)Hf(OiPr) 3 ;

(methylcyclopentadienyl)Hf(OtBu) 3 ;

(ethylcyclopentadienyl)Hf(OtBu) 3 ;

(propylcyclopentadienyl)Hf(OtBu) 3 ;

(methylcyclopentadienyl)Zr(OMe) 3 ;

(ethylcyclopentadienyl)Zr(OMe) 3 ;

(propylcyclopentadienyl)Zr(OMe) 3 ;

(methylcyclopentadienyl)Zr(OEt) 3 ;

(ethylcyclopentadienyl)Zr(OEt) 3 ;

(propylcyclopentadienyl)Zr(OEt) 3 ;

(methylcyclopentadienyl)Zr(OiPr) 3 ;

(ethylcyclopentadienyl)Zr(OiPr) 3 ;

(propylcyclopentadienyl)Zr(OiPr) 3 ;

(methylcyclopentadienyl)Zr(OtBu) 3 ;

(ethylcyclopentadienyl)Zr(OtBu) 3 ; and

(propylcyclopentadienyl)Zr(OtBu) 3 .

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

(methylcyclopentadienyl)Hf(OtBu) 3 ; and

(methylcyclopentadienyl)Zr(OtBu) 3 .

10. The method of claim 1 , wherein the atomic layer deposition comprises photo-assisted atomic layer deposition.

11. The method of claim 1 , wherein the atomic layer deposition comprises liquid injection atomic layer deposition.

12. The method of claim 1 , wherein the precursor is deposited onto 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 , further comprising depositing at least one appropriate co-reactant selected from the group consisting of hydrogen, hydrogen plasma, oxygen, air, water, ammonia, hydrazines, alkylhydrazines, boranes, silanes, ozone and a combination thereof.

15. The method of claim 1 , wherein at least two precursors corresponding in structure to Formula II are delivered to the substrate to form a metal-containing film by atomic layer deposition.

16. The method of claim 1 , further comprising delivering to the substrate at least one co-precursor to form a mixed metal film by atomic layer deposition.

17. The method of claim 16 , wherein the mixed metal film formed is selected from the group consisting of oxides and nitrides of hafnium, zirconium, titanium, lanthanum and any other lanthanide-series metal, and lead zirconate titanate.

18. The method of claim 1 , wherein the metal-containing film is used for a memory and/or logic application.

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

wherein:

M is Hf or Zr;

R is C 1 -C 6 -alkyl;

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

L is amino, wherein the amino is optionally independently substituted 1 or 2 times with C 1 -C 6 -alkyl.

20. The method of claim 19 , wherein

M is Hf or Zr;

R is C 1 -C 6 -alkyl;

n is 1 or 2;

L is amino, wherein the amino is optionally independently substituted 1 or 2 times with C 1 -C 6 -alkyl.

21. The method of claim 19 , wherein

M is Hf or Zr;

R is C 1 -C 6 -alkyl;

n is 3, 4 or 5;

L is amino, wherein the amino is optionally independently substituted 1 or 2 times with C 1 -C 6 -alkyl.

22. The method of claim 19 , wherein the at least one precursor corresponding in structure to Formula III is selected from the group consisting of (methylcyclopentadienyl)Hf(NMe 2 ) 3 ; and (methylcyclopentadienyl)Zr(NMe 2 ) 3 .

23. The method of claim 19 , wherein the at least one precursor corresponding in structure to Formula III is dissolved in a solvent prior to delivery to the substrate.

24. The method of claim 19 , wherein the at least one precursor corresponding in structure to Formula III is delivered neat to the substrate.

25. The method of claim 19 , further comprising utilizing photo-assisted ALD to form the metal containing film.