Methods for depositing a hafnium lanthanum oxide film on a substrate by a cyclical deposition process in a reaction chamber
A method for depositing a hafnium lanthanum oxide film on a substrate by a cyclical deposition in a reaction chamber is disclosed. The method may include: depositing a hafnium oxide film on the substrate utilizing a first sub-cycle of the cyclical deposition process and depositing a lanthanum oxide film utilizing a second sub-cycle of the cyclical deposition process.
1. A method for depositing a hafnium lanthanum oxide film on a substrate by a cyclical deposition process in a reaction chamber, the method comprising:
depositing a hafnium oxide film on the substrate utilizing at least one deposition cycle of a first sub-cycle of the cyclical deposition process, wherein the at least one deposition cycle of the first sub-cycle comprises:
contacting the substrate with a hafnium vapor phase precursor; and
contacting the substrate with a first oxidizer precursor comprising water (H 2 O);
depositing a lanthanum oxide film on the substrate utilizing at least one deposition cycle of a second sub-cycle of the cyclical deposition process, wherein the at least one deposition cycle of the second sub-cycle comprises:
contacting the substrate with a lanthanum vapor phase precursor; and
contacting the substrate with a second oxidizer precursor comprising molecular oxygen (O 2 );
wherein the cyclical deposition process comprises varying a ratio of a number of performed first sub-cycles to a number of performed second sub-cycles, and wherein the ratio of second sub-cycles performed to first sub-cycles performed per super-cycle is less than 0.2.
2. The method of claim 1 , wherein the hafnium vapor phase precursor comprises at least one of a hafnium halide precursor or a hafnium metalorganic precursor.
3. The method of claim 2 , wherein the hafnium halide precursor comprises at least one of hafnium tetrachloride (HfCl 4 ), hafnium tetraiodide (HfI 4 ), or hafnium tetrabromide (HfBr 4 ).
4. The method of claim 2 , wherein the hafnium metalorganic precursor comprises at least one of tetrakis(ethylmethylamido)hafnium (Hf(NEtMe) 4 ), tetrakis(dimethylamido)hafnium (Hf(NMe 2 ) 4 ), tetrakis(diethylamido)hafnium (Hf(NEt 2 ) 4 ), tris(dimethylamido)cyclopentadienylhafnium (HfCp(NMe 2 ) 3 ), or bis(methylcyclopentadienyl)methoxymethyl hafnium ((MeCp) 2 Hf(CH) 3 (OCH 3 )).
5. The method of claim 1 , wherein the lanthanum vapor phase precursor comprises at least one of a lanthanum amidinate or a lanthanum cyclopentadienyl compound.
6. The method of claim 1 , wherein, prior to the depositing of the hafnium oxide film on the substrate, heating the substrate to a temperature of from 100° C. to 400° C.
7. The method of claim 1 , wherein the lanthanum composition uniformity in the hafnium lanthanum oxide film is less than 2 atomic-% (1-sigma).
8. The method of claim 1 , wherein the hafnium lanthanum oxide film has a lanthanum composition of less than 10 atomic-%.
9. The method of claim 1 , wherein the hafnium lanthanum oxide film has a thickness of less than 20 nanometers.
10. The method of claim 9 , wherein the hafnium lanthanum oxide film has a thickness between 3 nanometers and 10 nanometers.
11. The method of claim 1 , wherein the second oxidizer precursor comprises molecular oxygen (O 2 ) with a purity greater than 99.999%.
12. The method of claim 1 , wherein the first oxidizer precursor comprises water with an electrical resistivity of greater than 5 MΩ-cm.
13. The method of claim 1 , wherein the hafnium oxide film is deposited to a thickness of less than 3 nanometers, and wherein the lanthanum oxide film is deposited to a thickness of less than 3 nanometers.
14. The method of claim 1 , wherein the hafnium lanthanum oxide film comprises a tertiary hafnium lanthanum oxide film.
15. The method of claim 1 , further comprising thermally annealing the hafnium lanthanum oxide film following depositing of the hafnium lanthanum oxide film at a temperature of less than 800° C.
16. The method of claim 15 , wherein thermally annealing the hafnium lanthanum oxide film further comprises at least partially crystallizing the hafnium lanthanum oxide film.
17. The method of claim 16 , wherein the hafnium lanthanum oxide film comprises a composition of lanthanum of equal to or less than 1 atomic-% with a crystallization temperature of less than approximately 600° C.
18. The method of claim 16 , wherein the at least partially crystallized hafnium lanthanum oxide film comprises a predominantly orthorhombic crystal structure.
19. The method of claim 1 , wherein the cyclical deposition process comprises one or more repeated super-cycles, each super-cycle including depositing the hafnium oxide film on the substrate and depositing the lanthanum oxide film on the substrate.
20. A method for depositing a hafnium lanthanum oxide film on a substrate by a cyclical deposition process in a reaction chamber, the method comprising:
depositing a hafnium oxide film on the substrate utilizing at least one deposition cycle of a first sub-cycle of the cyclical deposition process, wherein the at least one deposition cycle of the first sub-cycle comprises:
contacting the substrate with a hafnium vapor phase precursor; and
contacting the substrate with a first oxidizer precursor comprising water (H 2 O);
depositing a lanthanum oxide film on the substrate utilizing at least one deposition cycle of a second sub-cycle of the cyclical deposition process, wherein the at least one deposition cycle of the second sub-cycle comprises:
contacting the substrate with a lanthanum vapor phase precursor; and
contacting the substrate with a second oxidizer precursor comprising molecular oxygen (O 2 );
wherein the lanthanum composition uniformity in the hafnium lanthanum oxide film is less than 2 atomic-% (1-sigma).