Methods for depositing a transition metal chalcogenide film on a substrate by a cyclical deposition process
Methods for depositing a transition metal chalcogenide film on a substrate by cyclical deposition process are disclosed. The methods may include, contacting the substrate with at least one transition metal containing vapor phase reactant comprising at least one of a hafnium precursor, or a zirconium precursor, and contacting the substrate with at least one chalcogen containing vapor phase reactant. Semiconductor device structures including a transition metal chalcogenide film deposited by the methods of the disclosure are also provided.
1. A method for depositing a transition metal chalcogenide film on a substrate by a cyclical deposition process, the method comprising:
contacting the substrate with at least one transition metal containing vapor phase reactant comprising at least one of a hafnium precursor, or a zirconium precursor; and
contacting the substrate with at least one chalcogen containing vapor phase reactant, wherein the temperature of the substrate during the contacting steps is below about 450° C.
2. The method of claim 1 , wherein the cyclical deposition process comprises atomic layer deposition.
3. The method of claim 1 , wherein the cyclical deposition process comprises cyclical chemical vapor deposition.
4. The method of claim 1 , wherein the hafnium precursor, or the zirconium precursor comprises at least one of a halide precursor, or a metalorganic precursor.
5. The method of claim 4 , wherein the halide precursor comprises at least one of hafnium tetrachloride (HfCl 4 ), or zirconium tetrachloride (ZrCl 4 ).
6. The method of claim 4 , wherein the metalorganic precursor comprises at least one of an alkylamide precursor, or a cyclopentadienyl-ligand containing precursor.
7. The method of claim 6 , wherein the alkylamide precursor comprises at least one of tetrakis(ethylmethylamido)hafnium (Hf(NEtMe) 4 ), or tetrakis(ethylmethylamido)zirconium (Zr(NEtMe) 4 ).
8. The method of claim 6 , wherein the cyclopentadienyl-ligand containing precursor comprises at least one of tris(dimethylamido)cyclopentadienylhafnium (HfCp(NMe 2 ) 3 ), bis(methylcyclopentadienyl)methoxymethylhafnium ((MeCp) 2 Hf(CH) 3 (OCH 3 )), tris(dimethylamido)cyclopentadienylzirconium (ZrCp(NMe 2 ) 3 ), or bis(methylcyclopentadienyl)methoxymethylzirconium ((MeCp) 2 Zr(CH) 3 (OCH 3 )).
9. The method of claim 1 , wherein the at least one chalcogen containing vapor phase reactant comprises hydrogen sulfide (H 2 S), hydrogen selenide (H 2 Se), dimethyl sulfide ((CH 3 ) 2 S), or dimethyl telluride (CH 3 ) 2 Te.
10. The method of claim 1 , further comprising flowing the chalcogen containing vapor phase reactant through a gas purifier prior to entering the reaction chamber to reduce a concentration of at least one of water, or oxygen, within the chalcogen containing vapor phase reactant.
11. The method of claim 10 , wherein the concentration of at least one of water, or oxygen within the chalcogen containing vapor phase reactant is reduced to less than 1 part per million.
12. The method of claim 1 , further comprising flowing a carrier gas through a vessel containing a source of the transition metal containing vapor phase reactant to transport the transition metal containing vapor phase reactant to the reaction chamber and further comprising flowing the carrier gas through a gas purifier prior to entering the source of the transition metal containing vapor phase reactant to reduce a concentration of at least one of water, or oxygen, within the carrier gas.
13. The method of claim 12 , wherein the concentration of at least one of water, or oxygen within the carrier gas is reduced to less than 1 part per million.
14. The method of claim 1 , further comprising pre-annealing the reaction chamber prior to film deposition at a temperature of greater than 500° C.
15. The method of claim 1 , wherein the transition metal chalcogenide film comprises a predominant (001) crystallographic orientation.
16. The method of claim 1 , further comprising in-situ depositing a capping layer over the transition metal chalcogenide film to substantially prevent oxidation of the transition metal chalcogenide film when exposed to ambient conditions.
17. The method of claim 16 , wherein in-situ depositing a capping layer over the transition metal chalcogenide film further comprises depositing the capping layer utilizing non-oxidative precursors, or non-oxygen reactants.
18. The method of claim 16 , wherein the capping layer comprises a metal silicate film.
19. The method of claim 18 , wherein the metal silicate film comprises an aluminum silicate film (Al x Si y O z ).
20. A semiconductor device structure comprising a transition metal chalcogenide film deposited by the method of claim 1 .