Use of cyclopentadienyl type hafnium and zirconium precursors in atomic layer deposition
Precursors suitable for chemical vapor deposition, especially ALD, of hafnium oxide or zirconium oxide, have the general formula: (R 1 Cp) 2 MR 2 wherein Cp represents a cyclopentadienyl ligand, R 1 is H or a substituting alkyl group, alkoxy group or amido group of the Cp ligand, R 2 is an alkyl group, an alkoxy group or an amido group and M is hafnium or zirconium.
1. A method of depositing hafnium oxide or zirconium oxide by atomic layer deposition, the method comprising delivering a precursor to a substrate, wherein the precursor is delivered to the substrate in pulses alternating with pulses of an oxygen source and wherein the precursor has the general formula
(R 6 Cp) 2 MR 4 OR 5
wherein
Cp is a cyclopentadienyl ligand,
R 4 is an alkyl group or alkoxide group,
R 5 is an alkyl group,
R 6 is hydrogen or an alkyl group, and
M is hafnium or zirconium.
2. The method of claim 1 , wherein the oxygen source is selected from the group consisting of H 2 O, O 2 and ozone.
3. The method of claim 1 , wherein the precursor is delivered to the substrate by bubbling of carrier gas, vapor draw or other techniques using neat compounds.
4. The method of claim 1 , wherein a precursor compound solution is prepared and injected into an evaporator to put the precursor compound solution into the vapor phase for delivery to a growth chamber.
5. The method of claim 1 , wherein the method is used to deposit hafnium oxide or zirconium oxide on a silicon chip, wherein the silicon chip is used for memory and logic applications.
6. The method of claim 1 , wherein the precursor has the general formula
(R 6 Cp) 2 MR 4 OR 5
wherein
R 4 is a C 1 -C 4 -alkyl group or a C 1 -C 4 -alkoxide group,
R 5 is a C 1 -C 4 -alkyl group, and
R 6 is hydrogen or a C 1 -C 2 -alkyl group.
7. The method of claim 6 , wherein the precursor has the general formula
(R 6 Cp) 2 MR 4 OR 5
wherein
R 4 is a C 1 -C 2 -alkyl group or a C 1 -C 2 -alkoxide group,
R 5 is a C 1 -C 2 -alkyl group, and
R 6 is hydrogen or a C 1 -C 2 -alkyl group.
8. The method of claim 6 , wherein the precursor has the general formula
(R 6 Cp) 2 MR 4 OR 5
wherein
R 4 is a C 1 -C 2 -alkyl group,
R 5 is a C 1 -C 2 -alkyl group, and
R 6 is hydrogen or a C 1 -C 2 -alkyl group.
9. The method of claim 8 , wherein the precursor has the general formula
(R 6 Cp) 2 MR 4 OR 5
wherein
R 4 is methyl and R 5 is methyl.
10. The method of claim 6 , wherein the precursor has the general formula
(R 6 Cp) 2 MR 4 OR 5
wherein
R 4 is a C 1 -C 2 -alkoxide group,
R 5 is a C 1 -C 2 -alkyl group, and
R 6 is hydrogen or a C 1 -C 2 -alkyl group.
11. The method of claim 10 , wherein the precursor has the general formula
(R 6 Cp) 2 MR 4 OR 5
wherein
R 4 is methoxy and R 5 is methyl.
12. The method of claim 1 , wherein the precursor has the general formula
(R 6 Cp) 2 MR 4 OR 5
wherein
M is hafnium.
13. The method of claim 1 , wherein the precursor has the general formula
(R 6 Cp) 2 MR 4 OR 5
wherein
M is zirconium.
14. The method of claim 1 , wherein the precursor is bis(cyclopentadienyl) hafnium (IV) bis(methoxy).
15. The method of claim 1 , wherein the precursor is bis(methylcyclopentadienyl) hafnium (IV) bis(methoxy).
16. The method of claim 1 , wherein the precursor is bis(methylcyclopentadienyl) zirconium (IV) bis(methoxy).
17. The method of claim 1 , wherein the precursor is bis(methylcyclopentadienyl) hafnium (IV) methyl methoxy.
18. The method of claim 1 , wherein the precursor is bis(methylcyclopentadienyl) zirconium (IV) methyl methoxy.
19. A method of depositing hafnium oxide or zirconium oxide by atomic layer deposition, the method comprising delivering a precursor to a substrate, wherein the precursor is delivered to the substrate in pulses alternating with pulses of an oxygen source and wherein the precursor is bis(cyclopentadienyl) zirconium (IV) bis(methoxy).