Precursors for deposition of molybdenum-containing films
Molybdenum-containing films are deposited on semiconductor substrates using reactions of molybdenum-containing precursors in ALD and CVD processes. In some embodiments, the precursors can be used for deposition of molybdenum metal films with low levels of incorporation of carbon and nitrogen. In some embodiments, the films are deposited using fluorine-free precursors in a presence of exposed silicon-containing layers without using etch stop layers. The precursor, in some embodiments, is a compound that includes molybdenum, at least one halogen that forms a bond with molybdenum, and at chamber least one organic ligand that includes an element selected from the group consisting of N, O, and S, that forms a bond with molybdenum, In another aspect, the precursor is a molybdenum, compound with at least one sulfur-containing ligand, and preferably no molybdenum-carbon bonds.
1. A method of forming a molybdenum-containing layer on a semiconductor substrate, the method comprising:
(a) introducing a molybdenum-containing precursor into a process chamber housing the semiconductor substrate, wherein the molybdenum-containing precursor is Mo 2 L n , wherein each L is independently selected from the group consisting of an amidate, an amidinate and a guanidinate ligands, wherein n is 2-5, and wherein the molybdenum-containing precursor comprises a multiple molybdenum-molybdenum bond; and
(b) reacting the molybdenum-containing precursor to form a molybdenum-containing layer on the semiconductor substrate.
2. The method of claim 1 , wherein the molybdenum-containing layer is molybdenum metal.
3. The method of claim 1 , wherein the molybdenum-containing precursor is MO 2 L n , wherein each L is independently an amidinate or a guanidinate ligand, n is 2-5, wherein the amidinate ligand is:
wherein each R is independently selected from the group consisting of of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents, and wherein the the guanidinidate ligand is:
wherein each R is independently selected from the group consisting of of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents.
4. The method of claim 1 , wherein the molybdenum-containing precursor is Mo 2 L 3 or Mo 2 L 4 , wherein L is the amidinate.
5. The method of claim 1 , wherein the molybdenum-containing precursor is Mo 2 L 3 or Mo 2 L 4 , wherein L is a guanidinate.
6. The method of claim 1 , wherein (b) comprises reacting the molybdenum-containing precursor with hydrogen (H 2 ).
7. The method of claim 1 , wherein (b) comprises reacting the molybdenum-containing precursor with at least one reactant selected from the group consisting of hydrogen (H 2 ), ammonia (NH 3 ), diborane (B 2 H 6 ), water, H 2 S, a thiol, an alcohol, an amine, hydrazine, silane (SiH 4 ) and disilane (Si 2 H 6 ) to form a layer of molybdenum metal.
8. The method of claim 7 , wherein the molybdenum metal is deposited by thermal ALD or PEALD.
9. The method of claim 1 , wherein the molybdenum-containing layer is deposited conformally onto a substrate having a recessed feature.
10. A method of forming a molybdenum metal layer on a semiconductor substrate, the method comprising:
(a) introducing a molybdenum-containing precursor into a process chamber housing the semiconductor substrate, wherein the precursor is a compound that includes:
molybdenum;
at least one sulfur-containing ligand that forms molybdenum-sulfur bond with molybdenum, wherein the compound does not include molybdenum-carbon bonds, and wherein the at least one sulfur-containing ligand is a dithiolene, alpha iminothiolene, alpha dithiolate or beta dithiolate; and
(b) reacting the molybdenum-containing precursor to form molybdenum metal on the semiconductor substrate.
11. The method of claim 10 , wherein in the precursor molybdenum forms only molybdenum-sulfur bonds.
12. The method of claim 10 , wherein (b) comprises reacting the molybdenum-containing precursor with a reactant selected from the group consisting of hydrogen (H 2 ), ammonia (NH 3 ), diborane (B 2 H 6 ), water, H 2 S, a thiol, an alcohol, an amine, silane (SiH 4 ), disilane (Si 2 H 6 ), and hydrazine, to form a layer of molybdenum metal.
13. The method of claim 10 , wherein the reaction in (b) is conducted on a surface of the semiconductor substrate, and wherein the method comprises adsorbing the molybdenum-containing precursor onto the substrate and removing an unadsorbed molybdenum-containing precursor from the process chamber, prior to the reaction, reacting the adsorbed molybdenum-containing precursor with a reactant selected from the group consisting of water, an alcohol, H 2 S, and a thiol, and, after the reaction, treating the surface of the semiconductor substrate with hydrogen (H 2 ) with or without plasma to form the layer of molybdenum metal.
14. A precursor for deposition of molybdenum-containing films, wherein the precursor is Mo 2 L n , wherein each L is independently an amidinate or a guanidinate ligand, n is 2-5, and wherein the precursor comprises a multiple molybdenum-molybdenum bond, wherein the amidinate ligand is:
wherein each R is independently selected from the group consisting of of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents, and wherein the the guanidinidate ligand is:
wherein each R is independently selected from the group consisting of of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents.
15. A system for processing a semiconductor substrate, the system comprising:
(a) a processing chamber, having a substrate holder and one or more inlets for introduction of reactants to the processing chamber; and
(b) a system controller comprising program instructions for:
(i) causing an introduction of a molybdenum-containing precursor to the processing chamber, wherein the molybdenum-containing precursor is Mo 2 L n , wherein each L is independently selected from the group consisting of an amidate, an amidinate and a guanidinate ligands, wherein n is 2-5, and wherein the molybdenum-containing precursor comprises a multiple molybdenum-molybdenum bond; and
(ii) causing the molybdenum-containing precursor to react and form a molybdenum containing layer on the semiconductor substrate.
16. A system for processing a semiconductor substrate, the system comprising:
(a) a processing chamber, having a substrate holder and one or more inlets for introduction of reactants to the processing chamber; and
(b) a system controller comprising program instructions for:
(i) causing an introduction of a molybdenum-containing precursor to the processing chamber, wherein the molybdenum-containing precursor is a compound that includes:
molybdenum;
at least one sulfur-containing ligand that forms molybdenum-sulfur bond with molybdenum, wherein the compound does not include molybdenum-carbon bonds, and wherein the at least one sulfur-containing ligand is a dithiolene, alpha iminothiolene, alpha dithiolate or beta dithiolate; and
(ii) causing the molybdenum-containing precursor to react and form a molybdenum metal layer on the semiconductor substrate.