Silicon-containing surface modifier, resist underlayer film composition containing this, and patterning process
The present invention provides a silicon-containing surface modifier wherein the modifier contains one or more of a repeating unit shown by the following general formula (A) and a partial structure shown by the following general formula (C). The present invention has an object to provide a resist underlayer film applicable not only to a negatively developed resist pattern formed by a hydrophilic organic compound but also to a conventional positively developed resist pattern formed by a hydrophobic compound.
1. A silicon-containing resist underlayer film composition, comprising:
a polysiloxane compound as a base polymer; and
a silicon-containing surface modifier that contains one or more of a repeating unit shown by the following general formula (A) and a partial structure shown by the following general formula (C):
where in the formulae, R 1 represents an organic group having a hydroxyl group or a carboxylic acid group, the groups being substituted with an acid-labile group; and each of R 2 and R 3 independently represents a group identical to R 1 , a hydrogen atom, or a monovalent organic group having 1 to 30 carbon atoms,
wherein a blending amount of the silicon-containing surface modifier in the silicon-containing resist underlayer film composition is 0.1 to 10 parts by mass with respect to 100 parts by mass of the polysiloxane compound.
2. The silicon-containing resist underlayer film according to claim 1 , wherein the silicon-containing surface modifier further contains a repeating unit shown by the following general formula (B):
wherein R 1 and R 2 represent the same meanings as before.
3. The silicon-containing resist underlayer film according to claim 2 , wherein the acid-labile group in the foregoing R 1 is an acetal group or a tertiary alkyl group.
4. The silicon-containing resist underlayer film composition according to claim 3 , wherein, a content of a component derived from a four-functional hydrolysable monomer in the polysiloxane compound is 70 mole % or more.
5. The silicon-containing resist underlayer film composition according to claim 4 , wherein the silicon-containing resist underlayer film composition contains a solvent having a boiling point of 180° C. or higher.
6. The silicon-containing resist underlayer film composition according to claim 3 , wherein the silicon-containing resist underlayer film composition contains a solvent having a boiling point of 180° C. or higher.
7. The silicon-containing resist underlayer film composition according to claim 2 , wherein a content of a component derived from a four-functional hydrolysable monomer in the polysiloxane compound is 70 mole % or more.
8. The silicon-containing resist underlayer film composition according to claim 7 , wherein the silicon-containing resist underlayer film composition contains a solvent having a boiling point of 180° C. or higher.
9. The silicon-containing resist underlayer film composition according to claim 2 , wherein the silicon-containing resist underlayer film composition contains a solvent having a boiling point of 180° C. or higher.
10. The silicon-containing resist underlayer film according to claim 1 , wherein the acid-labile group in the foregoing R 1 is an acetal group or a tertiary alkyl group.
11. The silicon-containing resist underlayer film composition according to claim 10 , wherein a content of a component derived from a four-functional hydrolysable monomer in the polysiloxane compound is 70 mole % or more.
12. The silicon-containing resist underlayer film composition according to claim 11 , wherein the silicon-containing resist underlayer film composition contains a solvent having a boiling point of 180° C. or higher.
13. The silicon-containing resist underlayer film composition according to claim 10 , wherein the silicon-containing resist underlayer film composition contains a solvent having a boiling point of 180° C. or higher.
14. The silicon-containing resist underlayer film composition according to claim 1 , wherein a content of a component derived from a four-functional hydrolysable monomer in the polysiloxane compound is 70 mole % or more.
15. The silicon-containing resist underlayer film composition according to claim 14 , wherein the silicon-containing resist underlayer film composition contains a solvent having a boiling point of 180° C. or higher.
16. The silicon-containing resist underlayer film composition according to claim 1 , wherein the silicon-containing resist underlayer film composition contains a solvent having a boiling point of 180° C. or higher.
17. A patterning process, comprising:
forming an organic underlayer film on a body to be processed by using an application-type organic underlayer film composition;
forming a silicon-containing resist underlayer film on the organic underlayer film by using the silicon-containing resist underlayer film composition according to claim 1 ;
forming a photo resist film on the silicon-containing resist underlayer film by using a chemically amplifying type resist composition, and after applying heat treatment, exposing the photo resist film to a high energy beam;
forming a positive pattern by dissolving an exposed area of the photo resist film by using an alkaline developer;
transferring the pattern to the silicon-containing resist underlayer film by dry etching by using the photo resist film formed with the pattern as a mask;
transferring the pattern by dry etching the organic underlayer film by using the silicon-containing resist underlayer film transferred with the pattern as a mask; and then
transferring the pattern to the body to be processed by dry etching by using the organic underlayer film transferred with the pattern as a mask.
18. The patterning process according to claim 17 , wherein the body to be processed is a substrate for a semiconductor device or a substrate for a semiconductor device coated with any of a metal film, a metal alloy film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film.
19. The patterning process according to claim 18 , wherein the metal that constitutes the body to be processed is any of silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, aluminum, and iron, or a metal alloy thereof.
20. A patterning process, comprising:
forming an organic hard mask mainly composed of carbon on a body to be processed by a CVD method;
forming a silicon-containing resist underlayer film on the organic hard mask by using the silicon-containing resist underlayer film composition according to claim 1 ,
forming a photo resist film on the silicon-containing resist underlayer film by using a chemically amplifying type resist composition, and after applying heat treatment, exposing the photo resist film to a high energy beam;
forming a positive pattern by dissolving an exposed area of the photo resist film by using an alkaline developer;
transferring the pattern to the silicon-containing resist underlayer film by dry etching by using the photo resist film formed with the pattern as a mask;
transferring the pattern by dry etching the organic hard mask by using the silicon-containing resist underlayer film transferred with the pattern as a mask; and then
transferring the pattern to the body to be processed by dry etching by using the organic hard mask transferred with the pattern as a mask.
21. A patterning process, comprising:
forming an organic underlayer film on a body to be processed by using an application-type organic underlayer film composition;
forming a silicon-containing resist underlayer film on the organic underlayer film by using the silicon-containing resist underlayer film composition according to claim 1 ;
forming a photo resist film on the silicon-containing resist underlayer film by using a chemically amplifying type resist composition, and after applying heat treatment, exposing the photo resist film to a high energy beam;
forming a negative pattern by dissolving an unexposed area of the photo resist film by using an organic solvent developer;
transferring the pattern to the silicon-containing resist underlayer film by dry etching by using the photo resist film formed with the pattern as a mask;
transferring the pattern by dry etching the organic underlayer film by using the silicon-containing resist underlayer film transferred with the pattern as a mask; and then
transferring the pattern to the body to be processed by dry etching by using the organic underlayer film transferred with the pattern as a mask.
22. A patterning process, comprising:
forming an organic hard mask mainly composed of carbon on a body to be processed by a CVD method;
forming a silicon-containing resist underlayer film on the organic hard mask by using the silicon-containing resist underlayer film composition according to claim 1 ;
forming a photo resist film on the silicon-containing resist underlayer film by using a chemically amplifying type resist composition, and after applying heat treatment, exposing the photo resist film to a high energy beam;
forming a negative pattern by dissolving an unexposed area of the photo resist film by using an organic solvent developer;
transferring the pattern to the silicon-containing resist underlayer film by dry etching by using the photo resist film formed with the pattern as a mask;
transferring the pattern by dry etching the organic hard mask by using the silicon-containing resist underlayer film transferred with the pattern as a mask; and then
transferring the pattern to the body to be processed by dry etching by using the organic hard mask transferred with the pattern as a mask.