Films of desired composition and film properties
Provided are methods and systems for providing silicon-containing films. The composition of the silicon-containing film can be controlled by the choice of the combination of precursors and the ratio of flow rates between the precursors. The silicon-containing films can be deposited on a substrate by flowing two different organo-silicon precursors to mix together in a reaction chamber. The organo-silicon precursors react with one or more radicals in a substantially low energy state to form the silicon-containing film. The one or more radicals can be formed in a remote plasma source.
1. An apparatus ( 400 ) for depositing a silicon-carbon-containing film onto a substrate ( 430 ), the apparatus ( 400 ) comprising:
a reaction chamber ( 410 ) including a pedestal ( 435 ) for supporting a substrate ( 430 );
a precursor gas delivery source ( 450 ) configured to provide at least first and second organo-silicon precursors through one or more first gas inlets ( 455 ), wherein each of the first and second organo-silicon precursors comprises one or both of a silicon-silicon (Si—Si) bond and a silicon-hydrogen (Si—H) bond;
a plasma source ( 460 ) separate from the reaction chamber ( 410 ) and configured to generate hydrogen radicals from a source gas of hydrogen (H 2 );
a second gas inlet ( 465 ) for introducing the hydrogen radicals from the plasma source ( 460 ) into the reaction chamber ( 410 ); and
a controller ( 440 ) configured to control the plasma source ( 460 ), a flow of the first organo-silicon precursor, a flow of the second organo-silicon precursor, and the hydrogen radicals, wherein the controller ( 440 ) is configured with instructions to perform the following operations:
flow the first organo-silicon precursor into the reaction chamber ( 410 ) through the one or more first gas inlets ( 455 );
flow the second organo-silicon precursor into the reaction chamber ( 410 ) through the one or more first gas inlets ( 455 );
flow the hydrogen radicals into the reaction chamber ( 410 ) through the second gas inlet ( 465 ) so that the hydrogen radicals react with the first and second organo-silicon precursors to deposit the silicon-carbon-containing film on the substrate ( 430 ), wherein a composition of the silicon-carbon-containing film is modulated based at least in part on a chemistry of the second organo-silicon precursor, and wherein the second organo-silicon precursor further comprises one or both of a silicon-oxygen (Si—O) bond and a silicon-nitrogen (Si—N) bond.
2. The apparatus of claim 1 , wherein the controller ( 440 ) is configured to modulate relative atomic concentrations of silicon, carbon, oxygen, and nitrogen in the silicon-carbon-containing film based at least in part on a ratio of flow rates between the first organo-silicon precursor and the second organo-silicon precursor.
3. The apparatus of claim 1 , wherein the controller ( 440 ) is configured to modulate relative atomic concentrations of silicon, carbon, oxygen, and nitrogen in the silicon-carbon-containing film to tune at least one of the following film properties: a breakdown voltage, a leakage current, a dielectric constant, a hermeticity, a density, an adhesion to metal surfaces, an intrinsic stress, a Young's modulus, and a hardness.
4. The apparatus of claim 1 , wherein the controller ( 440 ) is configured to reduce a carbon concentration in the silicon-carbon-containing film to reduce a dielectric constant of the silicon-carbon-containing film.
5. The apparatus of claim 1 , wherein the first organo-silicon precursor comprises an organo-silicon oxide precursor, and wherein the silicon-carbon-containing film comprises an oxygen-doped silicon carbide film.
6. The apparatus of claim 1 , wherein the first organo-silicon precursor comprises an organo-silicon nitride precursor, and wherein the silicon-carbon-containing film comprises a nitrogen-doped silicon carbide film.
7. The apparatus of claim 1 , wherein the first organo-silicon precursor comprises an organo-silicon oxide precursor and the second organo-silicon precursor comprises an organo-silicon nitride precursor, and wherein the silicon-carbon-containing film comprises an oxygen-doped and nitrogen-doped silicon carbide film.
8. The apparatus of claim 1 , wherein the controller ( 440 ) is configured with instructions to perform the following: change a flow rate of the second organo-silicon precursor over time so that the hydrogen radicals react with the first and second organo-silicon precursors to deposit the silicon-carbon-containing film having varying relative atomic concentrations of silicon, carbon, oxygen, and nitrogen across a thickness of the silicon-carbon-containing film.
9. The apparatus of claim 1 , wherein the controller ( 440 ) is configured with instructions to perform the following operation: change a composition of the second organo-silicon precursor over time so that the hydrogen radicals react with the first and second organo-silicon precursors to deposit the silicon-carbon-containing film having varying relative atomic concentrations of silicon, carbon, oxygen, and nitrogen across a thickness of the silicon-carbon-containing film.
10. The apparatus of claim 1 , wherein the controller ( 440 ) is configured to flow the first and second organo-silicon precursors simultaneously together into the reaction chamber ( 410 ).
11. The apparatus of claim 1 , wherein the controller ( 440 ) is configured to flow the first and second organo-silicon precursors sequentially into the reaction chamber ( 410 ).
12. An apparatus ( 400 ) for depositing a silicon-carbon-containing film onto a substrate ( 430 ), the apparatus comprising:
a reaction chamber ( 410 ) including a pedestal ( 435 ) for supporting a substrate ( 430 );
a precursor gas delivery source ( 450 ) configured to provide at least first and second organo-silicon precursors through one or more first gas inlets ( 455 ), wherein each of the first and second organo-silicon precursors comprises one or both of a silicon-silicon (Si—Si) bond and a silicon-hydrogen (Si—H) bond;
a plasma source ( 460 ) separate from the reaction chamber ( 410 ) and configured to generate hydrogen radicals, wherein the hydrogen radicals are generated from a source gas of hydrogen (H 2 );
a second gas inlet ( 465 ) for introducing the hydrogen radicals from the plasma source ( 460 ) into the reaction chamber ( 410 ); and
a controller ( 440 ) configured with instructions to perform the following operations:
flow the first organo-silicon precursor into the reaction chamber ( 410 ) through the one or more first gas inlets ( 455 );
flow the second organo-silicon precursor into the reaction chamber ( 410 ) through the one or more first gas inlets ( 455 ); and
flow the hydrogen radicals into the reaction chamber ( 410 ) through the second gas inlet ( 465 ) so that the hydrogen radicals react with the first and second organo-silicon precursors with sufficient energy to break Si—H bonds and Si—Si bonds but preserve at least one of Si—O bonds, Si—C bonds, or Si—N bonds to deposit the silicon-carbon-containing film on the substrate ( 430 ).
13. The apparatus of claim 12 , wherein the second gas inlet ( 465 ) is configured to direct the hydrogen radicals into the reaction chamber ( 410 ) in a direction that is transverse to a major surface of the substrate ( 430 ).
14. The apparatus of claim 12 , wherein a distance between the plasma source ( 360 ) and the substrate ( 430 ) is configured so that the environment adjacent to the substrate ( 430 ) comprises hydrogen radicals in a ground state and so that the environment adjacent to the substrate ( 430 ) is free or substantially free of ions and ultraviolet (UV) radiation.
15. The apparatus of claim 14 ,
wherein the controller ( 440 ) is configured to control the plasma source ( 460 ), a flow of the first organo-silicon precursor, a flow of the second organo-silicon precursor, and the hydrogen radicals to cause the hydrogen radicals in the ground state to react with the first organo-silicon precursor and the second organo-silicon precursor to deposit the silicon-carbon-containing film.
16. The apparatus of claim 15 , wherein the controller ( 440 ) is further configured to modulate a composition of the silicon-carbon-containing film based at least in part on the flow or the first organo-silicon precursor relative to the flow of the second organo-silicon precursor.
17. The apparatus of claim 12 , wherein a distance that separates the second gas inlet ( 465 ) and the one or more first gas inlets ( 455 ) is between about 5 cm and about 20 cm.
18. The apparatus of claim 12 , wherein a distance between the plasma source ( 460 ) and the reaction chamber ( 410 ) is between about 10 cm and about 50 cm.
19. The apparatus of claim 12 , further comprising:
a vessel ( 470 ) coupled to the plasma source ( 460 ) configured to provide the source gas to the plasma source ( 460 ), wherein the second gas inlet ( 465 ) is coupled to the reaction chamber ( 410 ) via a showerhead assembly ( 420 ).
20. The apparatus of claim 19 , further comprising:
an RF power source ( 480 ) coupled to a controller ( 440 ), wherein the controller ( 440 ) is configured to control an RF power level via the RF power source ( 480 ) and a density of the source gas via the vessel ( 470 ) during generation of the hydrogen radicals in the plasma source ( 460 ).
21. The apparatus of claim 19 , wherein the showerhead assembly ( 420 ) includes a plurality of holes for distributing the hydrogen radicals into the reaction chamber ( 410 ).
22. The apparatus of claim 12 , wherein one or both of the first organo-silicon precursor and the second organo-silicon precursor comprises pentamethyldisiloxane (PMDSO) or tetramethyldisiloxane (TMDSO).
23. An apparatus ( 400 ) for depositing a silicon-carbon-containing film onto a substrate ( 430 ), the apparatus ( 400 ) comprising:
supporting means ( 435 ) for supporting the substrate ( 430 ) in a reaction chamber ( 410 );
remote plasma generating means ( 460 ) for generating a remote plasma separate from the reaction chamber ( 410 ), wherein the remote plasma comprises hydrogen radicals generated from a source gas of hydrogen (H 2 );
first delivery means ( 455 ) for delivering a first organo-silicon precursor into the reaction chamber ( 410 ), wherein the first organo-silicon precursor comprises one or both of a silicon-silicon (Si—Si) bond and a silicon-hydrogen (Si—H) bond, wherein the first delivery means ( 455 ) is located downstream of the remote plasma generating means ( 460 );
radicals delivery means ( 465 ) for delivering the hydrogen radicals into the reaction chamber ( 410 );
modulating means ( 455 ) for modulating a composition of the silicon-carbon-containing film with a second organo-silicon precursor, wherein the second organo-silicon precursor comprises one or both of a silicon-silicon (Si—Si) bond and a silicon-hydrogen (Si—H) bond and one or both of a silicon-oxygen (Si—O) bond and a silicon-nitrogen (Si—N) bond; and
a controller ( 440 ) configured with instructions for performing the following operations:
flow the first organo-silicon precursor into the reaction chamber ( 410 ) through the first delivery means ( 455 );
flow the second organo-silicon precursor into the reaction chamber ( 410 through the modulating means ( 455 ); and
flow the hydrogen radicals into the reaction chamber through the radicals delivery means ( 465 ) so that the hydrogen radicals react with the first organo-silicon precursor and the second organo-silicon precursor to deposit the silicon-carbon-containing film on the substrate ( 430 ).
24. The apparatus of claim 23 , wherein the radicals delivery means ( 465 ) is positioned from the modulating means ( 455 ) and the first delivery means ( 455 ) so that the conditions comprise hydrogen radicals in a ground state in an environment adjacent to the substrate ( 430 ).
25. The apparatus of claim 23 , wherein the radicals delivery means ( 465 ) positioned from the modulating means ( 455 ) and the first delivery means ( 455 ) so that the conditions are free or substantially free of ions in an environment adjacent to the substrate ( 430 ).
26. The apparatus of claim 23 , wherein the modulating means ( 455 ) modulates the composition of the silicon-carbon-containing film based at least in part on a flow rate of the second organo-silicon precursor relative to the first organo-silicon precursor.
27. The apparatus of claim 23 , wherein the modulating means ( 455 ) modulates the composition of the silicon-carbon-containing film so that the relative atomic concentrations of silicon, carbon, oxygen, and nitrogen in the silicon-carbon-containing film at an upper surface of the silicon-carbon-containing film are different than at a lower surface of the silicon-carbon-containing film.
28. The apparatus of claim 23 , wherein the first delivery means ( 455 ) flows the first organo-silicon precursor simultaneously together with the second organo-silicon precursor.
29. An apparatus ( 400 ) for depositing a silicon-carbon-containing film onto a substrate ( 430 ), the apparatus ( 400 ) comprising:
supporting means ( 435 ) for supporting the substrate ( 430 ) in a reaction chamber ( 410 );
remote plasma generating means ( 460 ) for generating a remote plasma separate from the reaction chamber ( 410 ), wherein the remote plasma comprises hydrogen radicals generated from a source gas of hydrogen (H 2 );
first delivery means ( 455 ) for delivering a first organo-silicon precursor into the reaction chamber ( 410 ), wherein the first organo-silicon precursor comprises one or both of a silicon-silicon (Si—Si) bond and a silicon-hydrogen (Si—H) bond;
second delivery means ( 455 ) for delivering a second organo-silicon precursor into the reaction chamber ( 410 ), wherein the second organo-silicon precursor comprises one or both of a silicon-silicon (Si—Si) bond and a silicon-hydrogen (Si—H) bond, wherein the second organo-silicon precursor has a different chemistry than the first organo-silicon precursor, and wherein the first and second delivery means ( 455 ) are located downstream of the remote plasma generating means ( 460 );
radicals delivery means ( 465 ) for delivering the hydrogen radicals into the reaction chamber ( 410 ); and
a controller ( 440 ) configured with instructions for performing the following operations:
flow the first organo-silicon precursor into the reaction chamber ( 410 ) through the first delivery means ( 455 );
flow the second organo-silicon precursor into the reaction chamber ( 410 ) through the second delivery means ( 455 );
flow the hydrogen radicals into the reaction chamber ( 410 ) through the radicals delivery means ( 465 ) so that the hydrogen radicals react with the first organ-silicon precursor and the second organo-silicon precursor to deposit the silicon-carbon-containing film on the substrate ( 430 ); and
change a ratio of flow rates between the first organo-silicon precursor and the second organo-silicon precursor over time during deposition of the silicon-carbon-containing film, wherein a composition of silicon-carbon-containing film varies across a thickness of the silicon-carbon-containing film.
30. The apparatus of claim 29 , wherein the silicon-carbon-containing film has a varying concentration of oxygen and nitrogen between an upper surface and a lower surface of the silicon-carbon-containing film.