Methods of atomic layer deposition for selective film growth
Methods of forming metal-containing films by atomic layer deposition are provided. The methods include delivering a metal-containing complex, a purge gas, and a co-reactant to a first substrate under sufficient conditions such that the metal-containing film selectively grows on at least a portion of the first substrate.
1. A method of forming a metal-containing film by atomic layer deposition, wherein the method comprises delivering a metal-containing complex, a purge gas, and a co-reactant to a first substrate under conditions sufficient for the metal-containing complex to:
(i) deposit metal and etch the metal-containing film;
(ii) deposit metal, etch the metal-containing film and allow for desorption from the metal-containing film; or
(iii) deposit metal and allow for desorption from the metal-containing film;
such that the metal-containing film selectively grows on at least a portion of the first substrate; and
wherein the conditions comprise a super-conformal growth cycle sufficient for the metal-containing film to selectively grow on a lower portion of a feature in the first substrate.
2. The method of claim 1 , wherein the co-reactant:
(i) deposits metal and etches the metal-containing film;
(ii) deposits metal, etches the metal-containing film and allows for desorption from the metal-containing film; or
(iii) deposits metal and allows for desorption from the metal-containing film.
3. The method of claim 1 , wherein (i) a deposition rate of the metal-containing complex is higher in a lower portion of the feature than in an upper portion of the feature and/or (ii) an etching rate and/or a desorption rate of the metal-containing complex is higher in an upper portion of the feature than in a lower portion of the feature.
4. The method of claim 1 , wherein the feature has one or more of:
(i) a depth ≥about 5 nm;
(ii) a non-uniform width;
(iii) a width ≤about 1000 nm;
(iv) about 5.0% to about 100% of the feature is filled; and
(v) substantially no voids within the feature.
5. The method of claim 1 , wherein the feature has one or more of:
(i) a depth of about 5 nm to about 3000 nm;
(ii) is wider at a lower portion compared to an upper portion of the feature; and
(iii) a width of about 1 nm to about 1000 nm.
6. The method of claim 1 , wherein the conditions further comprise one or more of:
a conformal growth cycle comprising delivering the metal-containing complex, the purge gas and the co-reactant to the substrate under conformal conditions, wherein the conformal growth cycle comprises a first series of one or more conformal growth cycles;
a sub-conformal growth cycle comprising delivering the metal-containing complex, the purge gas and the co-reactant to the substrate under sub-conformal conditions, wherein the sub-conformal growth cycle comprises a third series of one or more sub-conformal growth cycles; and
an etch cycle comprising delivering the metal-containing complex and the purge gas to the substrate under etching conditions, wherein the etch cycle comprises a fourth series of one or more etch cycles; and
wherein the super conformal growth cycle comprises a second series of one or more super-conformal growth cycles.
7. The method of claim 6 , wherein:
the first series of conformal growth cycles comprises 1 to 10 cycles;
the third series of sub-conformal growth cycles comprises 1 to 10 cycles;
the fourth series of etch cycles comprises 1 to 10 cycles; and
the second series of super conformal growth cycles comprises 1 to 10 cycles.
8. The method of claim 1 , wherein the film selectively grows on at least a portion of the first substrate over a second substrate.
9. The method of claim 8 , wherein the first substrate has a different deposition to etch/desorption ratio than the second substrate.
10. The method of claim 8 , wherein the duration of delivery of the purge gas is varied between delivering the metal-containing complex and the co-reactant such that growth is promoted on the first substrate while growth is inhibited on the second substrate.
11. The method of claim 8 , wherein the first substrate and the second substrate are each independently selected from the group consisting of silica, titanium nitride and molybdenum.
12. The method of claim 1 , wherein the metal-containing film has a root mean square roughness of less than 1.5 nm, or less than 5% of the film's thickness; or wherein the metal-containing film has a root mean square roughness of less than 0.8 nm, or less than 2% of the film's thickness.
13. The method of claim 1 , wherein the metal-containing complex comprises:
a metal selected from the group consisting of a transition metal, a lanthanide metal, an actinide metal, aluminum, gallium, indium, silicon, germanium, tin, lead, arsenic, antimony, bismuth, selenium, and tellurium; and
one or more ligands selected from the group consisting of a halogen, an alkoxy, an amidinate, a dialkyl-amide, an alkyl-sulfide, a dialkyl phosphide, an N,N′-dialkylamidinate, a cyclopentadienyl optionally substituted with at least one alkyl and/or at least one silyl, a carboxylate, an imide, an acetylacetonate, a hydride, a diketiminate, a mono-iminoketiminate, a trialkylsilyl, trihydrosilyl, a dialkylhydrosilyl, alkyldihydrosilyl, trialkylgermanyl, trihydrogermanyl, dialkylhydrogermanyl, alkyldihydrogermanyl, trialkylstannyl, trihydrostannyl, alkyldihydrostannyl, an amide optionally substituted with at least one silyl, a siloxy, a formamidinate optionally substituted with one or more hydride, alkyl and/or silyl, a acetamidinate optionally substituted with one or more hydride, alkyl and/or silyl, and a combination thereof.
14. The method of claim 13 , wherein the transition metal is selected from the group consisting of Mo, W, V, Nb, Fe, Ti, Ta, Co, and Ni; and/or wherein the metal-containing complex comprises one or more halogen ligands.
15. The method of claim 1 , wherein the metal-containing complex is MoCl 5 .
16. The method of claim 1 , wherein the purge gas comprises an inert gas and/or hydrogen.
17. The method of claim 1 , wherein the co-reactant is selected from the group consisting of:
1,4-bis-trimethylsilyl-2-methyl-cyclohexa-2,5-diene, 1-trimethylsilylcyclohexa-2,5-diene, and 1,4-bis-trimethylsilyl-1,4-dihydropyrazine.
18. A method of forming a metal-containing film by atomic layer deposition, wherein the method comprises delivering a metal-containing complex, a purge gas, and a co-reactant to a first substrate under conditions sufficient for the metal-containing complex to:
(i) deposit metal and etch the metal-containing film;
(ii) deposit metal, etch the metal-containing film and allow for desorption from the metal-containing film; or
(iii) deposit metal and allow for desorption from the metal-containing film;
such that the metal-containing film selectively grows on at least a portion of the first substrate;
wherein the conditions comprise one or more of:
(i) a conformal growth cycle comprising delivering the metal-containing complex, the purge gas and the co-reactant to the substrate under conformal conditions;
(ii) a super-conformal growth cycle comprising delivering the metal-containing complex, the purge gas and the co-reactant to the substrate under super-conformal conditions; and
(iii) a sub-conformal growth cycle comprising delivering the metal-containing complex, the purge gas and the co-reactant to the substrate under sub-conformal conditions.
19. The method of claim 18 , wherein the metal-containing film has a root mean square roughness of less than 1.5 nm, or less than 5% of the film's thickness; or wherein the metal-containing film has a root mean square roughness of less than 0.8 nm, or less than 2% of the film's thickness.
20. The method of claim 18 , wherein the conditions further comprise:
an etch cycle comprising delivering the metal-containing complex and the purge gas to the substrate under etching conditions.