Superplanarizing spin-on carbon materials
Planarizing and spin-on-carbon (SOC) compositions that fill vias and/or trenches on a substrate while planarizing the surface in a single thin layer coating process are provided. The compositions can planarize wide ranges of substrates with vias or trenches of from about 20 nm to about 220 nm wide, and up to about 700 nm deep. These extraordinary properties come from the low molecular weight of the polymers used in the materials, thermally-labile protecting groups on the polymers, and a delayed crosslinking reaction.
1. A method of forming a planarizing layer, said method comprising:
forming an initial layer of a planarizing composition on a substrate surface, said substrate surface comprising openings formed therein, said planarizing composition comprising a compound dispersed or dissolved in a solvent system, said compound comprising protective groups and said initial layer having an initial positive bias; and
heating said initial layer, during which said protective groups begin to be removed from said compound to form a deprotected compound and said deprotected compound crosslinks to form a final planarizing layer, said final planarizing layer being formed without a develop-back step after said heating and having a final bias that is less than said initial bias and less than about 30 nm, wherein:
the initial bias and the final bias are determined by subtracting the average thickness of the initial layer or of the final planarizing layer, respectively, over a dense region from the average thickness of that same layer over an open area region;
a dense region is a portion of a substrate that has at least about 50% of its surface area filled with via holes or a 1:1 line to space ratio; and
an open area region is a portion of a substrate that has less than about 20% of its surface area filled with via holes or a 1:5 line to space ratio.
2. The method of claim 1 , wherein said compound is selected from the group consisting of polymers and small molecules.
3. The method of claim 2 , wherein said compound is a polymer comprising recurring monomers (I) that comprise said protective groups.
4. The method of claim 3 , said polymer further comprising recurring monomers (II).
5. The method of claim 3 , said polymer further comprising recurring monomers (III), wherein said recurring monomers (III) comprise functional groups that can crosslink with recurring monomers (I) after said protective groups are removed.
6. The method of claim 5 , wherein said recurring monomers (I) comprise respective hydroxy groups that have been protected by said protective groups, said protective groups being removed during said heating to generate deprotected hydroxy groups that crosslink with said recurring monomers (III) during said heating.
7. The method of claim 3 , wherein said polymer further comprises recurring monomers (II) and (III).
8. The method of claim 3 , wherein said polymer further comprises recurring monomers (II) and said composition further comprises a crosslinking agent.
9. The method of claim 1 , wherein said planarizing composition has an initial surface tension, prior to said heating, and wherein said surface tension changes during said heating so as to create a surface tension gradient, said surface tension gradient causing said planarizing composition to flow toward, or toward and onto, said openings.
10. The method of claim 1 , wherein said compound has an initial polarity prior to said heating, and during said heating, the formed deprotected compound has a second polarity that is more polar than said initial polarity.
11. The method of claim 1 , wherein no additional or separate coating or heating is carried out to form said final planarizing layer, or to form additional planarizing layers.
12. The method of claim 1 , wherein at least about 50% of said protective groups are removed after about 30 seconds of heating at a temperature of from about 120° C. to about 260° C.
13. The method of claim 12 , wherein said crosslinking does not commence until at least about 5 seconds after said protective group removal commences.
14. The method of claim 1 , wherein said crosslinking does not commence until at least about 5 seconds after said protective group removal commences.
15. The method of claim 1 , wherein said compound comprises a hydroxy group that has been protected by said protective group.
16. The method of claim 15 , wherein said compound is a polymer comprising recurring monomers (I) that comprise a hydroxy group that has been protected by said protective group.
17. The method of claim 15 , wherein said protective groups being removed during said heating generate deprotected hydroxy groups.
18. The method of claim 17 , wherein said deprotected hydroxy groups are crosslinked during said heating.
19. The method of claim 1 , wherein said protective groups are selected from the group consisting of
and combinations of the foregoing, where R 5 is selected from the group consisting of alkyls.
20. The method of claim 1 , wherein said planarizing composition further comprises a crosslinking agent.
21. The method of claim 20 , wherein said compound comprises respective hydroxy groups that have been protected by said protective groups, said protective groups being removed during said heating to generate deprotected hydroxy groups that crosslink with said crosslinking agent during said heating.
22. A method of forming a planarizing layer, said method comprising:
forming an initial layer of a planarizing composition on a substrate surface, said substrate surface comprising openings formed therein, said planarizing composition comprising a polymer dispersed or dissolved in a solvent system, said polymer comprising recurring monomers (I) comprising protective groups and said initial layer having an initial bias; and
heating said initial layer, during which said protective groups begin to be removed from said recurring monomers (I) to form deprotected recurring monomers (I) that crosslink to form a final planarizing layer, said final planarizing layer having a final bias and being formed without a develop-back step after said heating, said final bias being less than said initial bias and less than about 30 nm, wherein:
the initial bias and the final bias are determined by subtracting the average thickness of the initial layer or of the final planarizing layer, respectively, over a dense region from the average thickness of that same layer over an open area region;
a dense region is a portion of a substrate that has at least about 50% of its surface area filled with via holes or a 1:1 line to space ratio; and
an open area region is a portion of a substrate that has less than about 20% of its surface area filled with via holes or a 1:5 line to space ratio.
23. The method of claim 22 , wherein said planarizing composition has an initial surface tension, prior to said heating, and wherein said surface tension changes during said heating so as to create a surface tension gradient, said surface tension gradient causing said planarizing composition to flow toward, or toward and onto, said openings.
24. The method of claim 22 , wherein said recurring monomers (I) have an initial polarity prior to said heating, and during said heating, the deprotected recurring monomers (I) have a second polarity that is more polar than said initial polarity.
25. The method of claim 22 , wherein no additional or separate coating or heating is carried out to form said final planarizing layer, or to form additional planarizing layers.
26. The method of claim 22 , wherein at least about 50% of said protective groups are removed after about 30 seconds of heating at a temperature of from about 120° C. to about 260° C.
27. The method of claim 22 , wherein said crosslinking does not commence until at least about 5 seconds after said protective group removal commences.
28. The method of claim 22 , wherein said recurring monomers (I) comprise a hydroxy group that has been protected by said protective group.
29. The method of claim 28 , wherein said protective groups being removed during said heating generates deprotected hydroxy groups.
30. The method of claim 29 , wherein said deprotected hydroxy groups are crosslinked during said heating.
31. The method of claim 22 , said polymer further comprising recurring monomers (II).
32. The method of claim 22 , said polymer further comprising recurring monomers (III), wherein said recurring monomers (III) comprise functional groups that can crosslink with recurring monomers (I) after said protective groups are removed.
33. The method of claim 32 , wherein said recurring monomers (I) comprise respective hydroxy groups that have been protected by said protective groups, said protective groups being removed during said heating to generate deprotected hydroxy groups that crosslink with said recurring monomers (III) during said heating.
34. The method of claim 22 , wherein said planarizing composition further comprises a crosslinking agent.
35. The method of claim 34 , wherein said recurring monomers (I) comprise respective hydroxy groups that have been protected by said protective groups, said protective groups being removed during said heating to generate deprotected hydroxy groups that crosslink with said crosslinking agent during said heating.