Low temperature flowable vanadium oxide gap fill
Vapor deposition methods and related systems are provided for depositing layers comprising vanadium and oxygen. In some embodiments, the methods comprise contacting a substrate in a reaction space with alternating pulses of a vapor-phase vanadium precursor and a vapor-phase oxygen reactant. The reaction space may be purged, for example, with an inert gas, between reactant pulses. The methods may be used to fill a gap on a substrate surface. Reaction conditions, including deposition temperature and reactant pulse and purge times may be selected to achieve advantageous gap fill properties. In some embodiments, the substrate on which deposition takes place is maintained at a relatively low temperature, for example between about 50° C. and about 185° C.
1 . A vapor deposition process comprising:
providing a substrate on a susceptor in a reaction space, wherein the substrate comprises a gap comprising a distal part and a proximal part, wherein the substrate comprises a first material, and wherein both the distal part and the proximal part of the gap comprise the first material; and
depositing vanadium oxide on the substrate by a plurality of vapor deposition cycles comprising:
contacting the substrate with a vapor-phase vanadium precursor by pulsing the vapor-phase vanadium precursor into the reaction space for about 0.05 to about 0.2 seconds;
purging excess vapor-phase vanadium precursor from the reaction space; and
contacting the substrate with a vapor-phase oxygen reactant by pulsing the vapor-phase oxygen reactant into the reaction space for about 0.1 to about 0.5 seconds,
wherein the susceptor is maintained at a temperature of between about 50° C. and about 185° C. during the plurality of vapor deposition cycles, and
wherein the vanadium oxide is deposited preferentially in the distal part relative to the proximal part of the gap in the substrate.
2 . The vapor deposition process of claim 1 , wherein the susceptor is maintained at a temperature of about 115° C. during the plurality of vapor deposition cycles.
3 . The vapor deposition process of claim 1 , additionally comprising purging excess oxygen reactant from the reaction space for a duration of about 0.1 to about 5 seconds.
4 . The vapor deposition process of claim 3 , wherein the duration is about 5 seconds.
5 . The vapor deposition process of claim 3 , wherein purging excess vapor-phase vanadium precursor comprises flowing an inert purge gas into the reaction space.
6 . The vapor deposition process of claim 1 , wherein the vapor deposition process is an atomic layer deposition process.
7 . The vapor deposition process of claim 1 , wherein the vapor-phase oxygen reactant comprises one or more of molecular oxygen (O 2 ), water (H 2 O), and hydrogen peroxide (H 2 O 2 ).
8 . The vapor deposition process of claim 1 , wherein the vapor-phase vanadium precursor comprises one or more of a vanadium halide, a vanadium oxyhalide, a vanadium beta-diketonate compound, a vanadium cyclopentadienyl compound, a vanadium alkoxide compound, a vanadium amidate compound, a vanadium alkylimido compound, and/or a vanadium dialkylamido compound.
9 . The vapor deposition process of claim 1 , wherein the vapor-phase vanadium precursor is VCl 4 and the vapor-phase oxygen reactant is H 2 O.
10 . The vapor deposition process of claim 1 , wherein the first material comprises at least one of silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, or silicon carbide.
11 . The vapor deposition process of claim 1 , wherein the gap on the substrate has an aspect ratio of between 2 and 10.
12 . A method of filling a gap on a substrate in a reaction space with vanadium oxide, the method comprising a plurality of vapor deposition cycles, comprising:
alternately and sequentially contacting the substrate with a vapor-phase vanadium precursor and an oxygen reactant, wherein the substrate is supported in the reaction space by a susceptor that is maintained at a temperature of between about 50° C. and about 185° C. during the plurality of vapor deposition cycles, wherein the contacting the substrate with the vapor-phase vanadium precursor comprises pulsing the vapor-phase vanadium precursor into the reaction space for about 0.05 to about 0.2 seconds, and wherein the contacting the substrate with the oxygen reactant comprises pulsing the oxygen reactant into the reaction space for about 0.1 to about 0.5 seconds, wherein the gap comprises a distal part and a proximal part, both of which comprise a first material, and wherein the vanadium oxide is deposited preferentially in the distal part relative to the proximal part.
13 . The method of claim 12 , wherein the first material comprises at least one of silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, or silicon carbide.
14 . The method of claim 12 , wherein the gap on the substrate has an aspect ratio of between 2 and 10.
15 . The method of claim 12 , wherein the gap in the substrate is filled without substantially forming any seams or voids.
16 . The method of claim 12 , wherein the vapor-phase vanadium precursor is VCl 4 and the oxygen reactant is H 2 O.
17 . A method of forming a gap fill layer, comprising:
providing a substrate comprising at least one opening formed thereon, wherein the at least one opening comprises a recessed pattern with an aspect ratio of between 2 and 10, wherein the at least one opening comprises a distal part and a proximal part, wherein the distal part and the proximal part both comprise a first material, wherein the substrate is supported on a susceptor and wherein a temperature of the susceptor is between about 50° C. and about 185° C.; and
depositing a material comprising vanadium oxide in the at least one opening by a thermal cyclic vapor deposition process comprising a plurality of vapor deposition cycles, wherein the vapor deposition cycles comprise exposing the substrate to a vanadium precursor comprising VCl 4 by pulsing the vanadium precursor into a reaction space for about 0.05 to about 0.2 seconds, exposing the substrate to an oxygen reactant comprising H 2 O by pulsing the oxygen reactant into the reaction space for about 0.1 to about 0.5 seconds, and an oxygen reactant purge, and
wherein the material comprising vanadium oxide is deposited preferentially in the distal part relative to the proximal part of the at least one opening in the substrate.
18 . The method of claim 17 , wherein the oxygen reactant purge has a duration of about 1 s to about 5 s.
19 . The method of claim 17 , wherein the first material comprises at least one of silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, or silicon carbide.