Selective area deposition of metal films by atomic layer deposition (ALD) and chemical vapor deposition (CVD)
US-9236292-B2 · Jan 12, 2016 · US
US9502289B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-9502289-B2 |
| Application number | US-201514737293-A |
| Country | US |
| Kind code | B2 |
| Filing date | Jun 11, 2015 |
| Priority date | Dec 9, 2011 |
| Publication date | Nov 22, 2016 |
| Grant date | Nov 22, 2016 |
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Metallic layers can be selectively deposited on one surface of a substrate relative to a second surface of the substrate. In some embodiments, the metallic layers are selectively deposited on copper instead of insulating or dielectric materials. In some embodiments, a first precursor forms a layer on the first surface and is subsequently reacted or converted to form a metallic layer. The deposition temperature may be selected such that a selectivity of above about 50% or even about 90% is achieved.
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What is claimed is: 1. A method for selectively depositing a film on a substrate comprising a first metal surface and a second dielectric surface, the method comprising: cleaning the substrate; forming a surface termination on the second dielectric surface; after cleaning carrying out one or more deposition cycles at a temperature of less than 150° C., each cycle comprising: contacting the substrate with a first precursor; and contacting the substrate with a second precursor comprising a metal, wherein deposition on the first metal surface relative to the second dielectric surface has a selectivity of greater than about 50%. 2. The method of claim 1 , wherein the one or more deposition cycles are carried out prior to forming the surface termination on the second dielectric surface. 3. The method of claim 1 , wherein the one or more deposition cycles are carried out after forming the surface termination on the second dielectric surface. 4. The method of claim 3 , wherein the cleaning is carried out after forming the surface termination on the second dielectric surface. 5. The method of claim 1 , wherein the surface termination is formed in a first reaction chamber and the one or more deposition cycles are carried out in a second, different reaction chamber. 6. The method of claim 1 , wherein the first precursor comprises Si or B. 7. The method of claim 1 , wherein the second precursor comprises a metal selected from W, Ta, Nb, Ti, Mo and V. 8. The method of claim 7 , wherein the second precursor comprises WF 6 . 9. The method of claim 1 , wherein cleaning comprises removing a passivation layer from the first metal surface. 10. The method of claim 1 , wherein cleaning comprises exposing the substrate to a plasma. 11. The method of claim 1 , wherein forming the surface termination comprises silylation of the second dielectric surface. 12. The method of claim 1 , wherein forming the surface termination comprises forming —Si(CH 3 ) 3 groups on the second dielectric surface. 13. The method of claim 1 , wherein the first metal surface comprises copper. 14. The method of claim 1 , wherein the film comprises a metal nitride or metal silicide. 15. The method of claim 1 , additionally comprising annealing the substrate after cleaning and prior to carrying out the one or more deposition cycles. 16. The method of claim 1 , wherein the method has a selectivity for depositing material on the first metal surface relative to the second dielectric surface of above about 90%. 17. A method for selectively depositing a film on a first metal surface of a substrate relative to a second dielectric surface of the substrate, the method comprising: conducting a dielectric restoration step; carrying out one or more deposition cycles at a temperature of less than 150° C., each cycle comprising alternately and sequentially contacting the substrate with a first precursor and a second precursor comprising a metal selected from W, Ta, Nb, Ti, Mo and V, wherein deposition on the first metal surface relative to the second dielectric surface is greater than about 50% selective. 18. The method of claim 17 , wherein the dielectric restoration step and the deposition cycles are conducted in different reaction spaces. 19. The method of claim 17 , wherein the dielectric restoration step comprises contacting the second dielectric surface with SiHxLy, where L is selected from alkyl, alkenyl, alkynyl, alkoxide and amide groups. 20. The method of claim 17 , wherein the dielectric restoration step comprises silylation of the second dielectric surface. 21. The method of claim 17 , wherein the dielectric restoration step comprises forming —Si(CH 3 ) 3 groups on the second dielectric surface. 22. The method of claim 17 , wherein the dielectric restoration step is conducted prior to conducting the one or more deposition cycles. 23. The method of claim 17 , wherein the selectivity is greater than about 90%. 24. The method of claim 17 , additionally comprising annealing the substrate at a temperature from 150° C. to 400° C. prior to conducting the deposition cycles. 25. The method of claim 17 , wherein an organic layer is formed on the dielectric surface prior to carrying out the one or more deposition cycles. 26. The method of claim 25 , wherein the organic layer makes the dielectric layer more resistant to metal fluorides. 27. The method of claim 17 , wherein the film is a metal nitride or metal silicide. 28. A method for selectively depositing a film on a substrate comprising a first metal surface and a second dielectric surface, the method comprising: cleaning the substrate; forming a surface termination on the second dielectric surface; after cleaning carrying out one or more deposition cycles at a temperature of less than 150° C., each cycle comprising: exposing the substrate to a first precursor; and exposing the substrate to a second precursor comprising a metal, wherein a thin film is selectively deposited on the first metal surface relative to the second dielectric surface and the selectivity is greater than about 50%. 29. The method of claim 28 , wherein the one or more cycles are carried out prior to forming a surface termination on the second dielectric surface. 30. The method of claim 28 , wherein the second precursor comprises a metal selected from W, Ta, Nb, Ti, Mo and V. 31. The method of claim 28 , wherein forming a surface termination comprises forming —Si(CH 3 ) 3 groups on the second dielectric surface.
Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass · CPC title
during, before or after processing of conductive materials, e.g. polysilicon or amorphous silicon layers · CPC title
using selective deposition · CPC title
the conductive layers comprising transition metals · CPC title
using conductive layers comprising silicides · CPC title
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