Substrate treating apparatus and substrate treating method
Disclosed is a substrate treating apparatus including the following units: a supplying unit which supplies a process liquid including a sublimable substance in a melt state on a pattern-formed surface of a substrate W; a solidifying unit which solidifies the process liquid on the pattern-formed surface to produce a solidified body; and a sublimating unit which sublimates the solidified body to remove the solidified body from the pattern-formed surface. In this apparatus, the sublimable substance includes a fluorinated carbon compound.
1. A substrate treating apparatus, comprising:
a supplying unit which supplies a process liquid comprising a sublimable substance in a melt state on a pattern-formed surface of a substrate;
a solidifying unit which solidifies the process liquid on the pattern-formed surface to produce a solidified body; and
a sublimating unit which sublimates the solidified body to remove the solidified body from the pattern-formed surface;
wherein the sublimable substance comprises a fluorinated carbon compound that at least one compound selected from the group consisting of the following compounds (A) to (E);
a compound (A): a fluoroalkane having 3 to 6 carbon atoms, or the fluoroalkane to which at least one selected from the group consisting of the following is bonded: halogen radicals except a fluorine radical, a hydroxide group, an oxygen atom, a carboxyl group, and a perfluoroalkyl groups;
a compound (B): a fluorocycloalkane having 3 to 6 carbon atoms, or the fluorocycloalkane to which at least one selected from the group consisting of the following is bonded: halogen radicals except a florine radical, a hydroxide group, an oxygen atom, a carboxyl group, and a perfluoroalkyl groups;
a compound (C): a fluorobicycloalkane having 10 carbon atoms, or the fluorobicycloalkane to which at least one selected from the group consisting of the following is bonded: halogen radicals except a fluorine radical, cycloalkyl groups which may each have a halogen atom, and alkyl groups each having a cycloalkyl group which may have a halogen atom;
a compound (D): a fluorotetracyanoquinodimethane, or the fluorotetracyanoquinodimethane to which at least one halogen radical except a fluorine radical is bonded; and
a compound (E): a fluorocyclotriphosphazene, or the fluorocyclotriphosphazene to which at least one selected from the group consisting of the following is bonded: halogen radicals except a fluorine radical, a phenoxy group, and alkoxy groups.
2. The substrate treating apparatus according to claim 1 ,
wherein the process liquid further comprises an alcohol showing compatibility with the sublimable substance, and
a concentration of the alcohol in the process liquid ranges from 0.001 to 0.8% by volume of the process liquid.
3. The substrate treating apparatus according to claim 2 ,
wherein the alcohol is isopropyl alcohol.
4. The substrate treating apparatus according to claim 1 ,
wherein the compound (A) is tetradecafluorohexane.
5. The substrate treating apparatus according to claim 1 ,
wherein the compound (B) is at least one compound selected from the group consisting of 1,1,2,2-tetrachloro-3,3,4,4-tetrafluorocyclobutane, 1,2,3,4,5-pentafluorocyclopentane, 1,1,2,2,3,3,4-heptafluorocyclopentane, fluorocyclohexane, dodecafluorocyclohexane, 1,1,4-trifluorocyclohexane, 2-fluorocyclohexanol, 4,4-difluorocyclohexanone, 4,4-difluorocyclohexanecarboxylic acid, and 1,2,2,3,3,4,4,5,5,6,6-undecafluoro-1-(nonafluorobutyl)cyclohexane.
6. The substrate treating apparatus according to claim 1 ,
wherein the compound (C) is 2-[difluoro(undecafluorocyclohexyl)methyl]-1,2,3,3,4,4,4a,5,5,6,6,7,7,8,8,8a-heptadecafluorodecahydronaphthalene.
7. The substrate treating apparatus according to claim 1 ,
wherein the compound (D) is tetrafluorotetracyanoquinodimethane.
8. The substrate treating apparatus according to claim 1 ,
wherein the compound (E) is hexafluorocyclotriphosphazene.
9. The substrate treating apparatus according to claim 1 ,
wherein the supplying unit is a unit which supplies the process liquid to the pattern-formed surface of the substrate under an atmospheric pressure, and
the solidifying unit is a unit which cools the process liquid under an atmospheric pressure to a temperature not higher than a solidifying point of the sublimable substance.
10. The substrate treating apparatus according to claim 1 ,
wherein the fluorinated carbon compound as the sublimable substance has sublimability under an atmospheric pressure, and
the sublimating unit sublimates the sublimable substance under the atmospheric pressure.
11. The substrate treating apparatus according to claim 10 ,
wherein the solidifying unit and the sublimating unit are a common gas supplying unit which supplies an inert gas chemically inert to at least the sublimable substance to the pattern-formed surface at a temperature not higher than a solidifying point of the sublimable substance.
12. The substrate treating apparatus according to claim 10 ,
wherein at least one of the solidifying unit and the sublimating unit is a unit which supplies a coolant to a back surface of the substrate, which is opposite to the pattern-formed surface of the substrate, at a temperature not higher than a solidifying point of the sublimable substance.
13. The substrate treating apparatus according to claim 1 ,
wherein the sublimating unit is a pressure reducing unit which makes an environment in which the pattern-formed surface, on which the solidified body is produced, is located into a pressure lower than an atmospheric pressure.
14. The substrate treating apparatus according to claim 13 ,
wherein as the solidifying unit, the pressure reducing unit is used.
15. The substrate treating apparatus according to claim 1 ,
wherein the supplying unit has a process liquid temperature adjusting part which adjusts a temperature of the process liquid to a temperature that is not lower than a melting point of the sublimable substance and is lower than the boiling point of the substance.
16. The substrate treating apparatus according to claim 1 ,
wherein the supplying unit is a unit which supplies the process liquid as a washing liquid or a rinsing liquid to the pattern-formed surface of the substrate to wash or rinse the pattern-formed surface.
17. The substrate treating apparatus according to claim 1 ,
further comprising a water repellent treatment unit which applies water repellent treatment to the pattern-formed surface of the substrate before the process liquid is supplied to the pattern-formed surface.
18. The substrate treating apparatus according to claim 2 ,
wherein the solidifying unit and the sublimating unit are a common gas supplying unit which supplies an inert gas chemically inert to at least the sublimable substance and the alcohol to the pattern-formed surface at a temperature not higher than a solidifying point of the process liquid.
19. The substrate treating apparatus according to claim 18 ,
wherein the supplying unit has a process liquid temperature adjusting part which adjusts the temperature of the process liquid to a temperature that is not lower than a melting point of the sublimable substance, and that is a temperature lower than lower one of the respective boiling points of the sublimable substance and the alcohol.
20. A substrate treating method, comprising:
a supplying step of supplying a process liquid comprising a sublimable substance in a melt state on a pattern-formed surface of a substrate;
a solidifying step of solidifying the process liquid on the pattern-formed surface to produce a solidified body; and
a sublimating step of sublimating the solidified body to be removed from the pattern-formed surface;
wherein the sublimable substance comprises a fluorinated carbon compound that is at least one compound selected from the group consisting of the following compounds (A) to (E):
a compound (A): a fluoroalkane having 3 to 6 carbon atoms, or the fluoroalkane to which at least one selected from the group consisting of the following is bonded: halogen radicals except a fluorine radical, a hydroxide group, an oxygen atom, a carboxyl group, and perfluoroalkyl groups;
a compound (B): a fluorocycloalkane having 3 to 6 carbon atoms, or the fluorobicycloalkane to which at least one selected from the group consisting of the following is bonded: halogen radicals except a fluorine radical, a hydroxide group, an oxygen atom, a carboxyl group, and the perfluoroalkyl groups;
a compound (C): a fluorobicycloalkane having 10 carbons, or the fluorobicycloalkane to which at least one selected from the group consisting of the following is bonded: halogen radicals except a fluorine radical, cycloalkyl groups which may each have a halogen atom, and alkyl groups each having a cycloalkyl group which may have halogen atom;
a compound (D): a fluorotetracyanoquinodimethane, or the fluorotetracyanoquinodimethane to which at least one halogen radical except a fluorine radical is bonded; and
a compound (E): a fluorocyclotriphosphazene, or the fluorocyclotriphosphazene to which at least one selected from the group consisting the of the following is bonded: halogen radicals except a fluorine radical, a phenoxy group, and alkoxy groups.
21. The substrate treating method according to claim 20 ,
wherein the process liquid further comprises an alcohol showing compatibility with the sublimable substance, and
a concentration of the alcohol in the process liquid ranges from 0.001 to 0.8% by volume of the process liquid.
22. The substrate treating method according to claim 21 ,
wherein the alcohol is isopropyl alcohol.
23. The substrate treating method according to claim 20 ,
wherein the compound (A) is tetradecafluorohexane.
24. The substrate treating method according to claim 20 ,
wherein the compound (B) is at least one compound selected from the group consisting of 1,1,2,2-tetrachloro-3,3,4,4-tetrafluorocyclobutane, 1,2,3,4,5-pentafluorocyclopentane, 1,1,2,2,3,3,4-heptafluorocyclopentane, fluorocyclohexane, dodecafluorocyclohexane, 1,1,4-trifluorocyclohexane, 2-fluorocyclohexanol, 4,4-difluorocyclohexanone, 4,4-difluorocyclohexanecarboxylic acid, and 1,2,2,3,3,4,4,5,5,6,6-undecafluoro-1-(nonafluorobutyl)cyclohexane.
25. The substrate treating method according to claim 20 ,
wherein the compound (C) is 2-[difluoro(undecafluorocyclohexyl)methyl]-1,1,2,3,3,4,4,4a,,5,5,6,6,7,7,8,8,8a-heptadecafluorodecahydronaphthalene.
26. The substrate treating method according to claim 20 ,
wherein the compound (D) is tetrafluorotetracyanoquinodimethane.
27. The substrate treating method according to claim 20 ,
wherein the compound (E) is hexafluorocyclotriphosphazene.