Silicone polymer composition, method of forming a pattern and method of forming an insulating film

• US 5,962,581 A
• Filed: 04/26/1996
• Issued: 10/05/1999
• Est. Priority Date: 04/28/1995
• Status: Expired due to Fees

• Current Assignee: Kabushiki Kaisha Toshiba (Toshiba Corporation)
• Original Assignee: Kabushiki Kaisha Toshiba (Toshiba Corporation)
• Inventors: Ito, Mao, Nakano, Yoshihiko, Mikoshiba, Satoshi, Hayase, Shuzi, Okino, Takeshi, Fujioka, Sawako, Kani, Rikako
• Primary Examiner(s): MOORE, MARGARET G
• Application Number:
  US08/638,698
• Time in Patent Office: 1,257 Days
• Field of Search: 528/10, 528/31, 528/21, 522/172, 522/63, 524/588, 524/443, 524/789, 427/493, 427/510, 427/515, 427/387, 430/326, 430/322, 430/920
• US Class Current: 524/588
• CPC Class Codes: C08K 3/36 Silica
• CPC Class Codes: C08K 5/0008 Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: Y10S 430/121 Nitrogen in heterocyclic ring

Abstract

A method of forming a pattern comprising the steps of forming a film of an organosilane compound comprising a polysilane having a repeating unit represented by the following general formula (1) on a substrate, irradiating an actinic radiation onto a predetermined portion of the film of the organosilane compound formed on the substrate, and removing the predetermined portion of the film irradiated by the actinic radiation by dissolving it with an aqueous alkaline developing solution. ##STR1## wherein Ar is a substituted or non-substituted aryl group.

Claims

1. A silicon polymer composition comprising a polysilane having a repeating unit represented by the following general formula (4) and at least one kind of powders selected from SiO₂ fine powder and SiN powder ##STR56## wherein R⁴ is a substituted or non-substituted aryl group, or a substituted or non-substituted alkyl group.

27. A method of forming an insulating film comprising the steps of:

forming a film of an organosilane compound comprising a silicon polymer composition of claim 1 on a substrate; and

heat-drying the film of the organosilane compound in an oxygen-containing atmosphere thereby to turn the film into a three-dimensional structure.

28. The method of forming an insulating film according to claim 27, wherein said heat-drying is performed at a temperature of 100 to 600°

C.

29. The method of forming an insulating film according to claim 27, which further comprises a step of irradiating the entire surface of said organosilane compound film in an oxygen-containing atmosphere prior to the heat-drying step of the organosilane compound film.

30. The silicon polymer composition according to claim 1, wherein the substituted aryl group Ar is substituted by alkyl, fluoroalkyl, bromine, alkoxy, hydroxy or cyano.

36. The method according to claim 27, wherein the substituted aryl group Ar is substituted by alkyl, fluoroalkyl, bromine, alkoxy, hydroxy or cyano.

2. A silicon polymer composition comprising a polysilane having a repeating unit represented by the following general formula (1) and not having a polymerizable multi-bond, and a compound which is capable of generating a radial or an acid as it is irradiated by an actinic radiation ##STR57## wherein Ar is a substituted or non-substituted aryl group, wherein said compound which is capable of generating a radical or an acid is an organic halogen compound represented by the general formula (2) shown below:

##STR58## wherein Q is bromine atom or chlorine atom;

P is CQ₃, -NH2, -NHR², -N(R²)₂, -OR² or a substituted or non-substituted phenyl group, wherein Q is as above defined;

R² is a phenyl group, naphthyl group or lower alkyl group having not more than 6 carbon atoms; and

R¹ is -CQ₃, -NH₂, -NHR², -N(R²)₂, -OR², -(CH=CH)_n -W or a substituted or non-substituted phenyl group, wherein Q and R² are as above defined, n is an integer of 1 to 3, W is an aromatic group, heterocyclic group or a group represented by the following general formula (3) ##STR59## wherein Z is an oxygen atom or a sulfur atom; and

R³ is a lower alkyl group or phenyl group.

3. A silicon polymer composition comprising a polysilane having a repeating unit represented by the following general formula (1) and not having a polymerizable multi-bond, and a compound which is capable of generating a radial or an acid as it is irradiated by an actinic radiation ##STR60## wherein Ar is a substituted or non-substituted aryl group wherein said compound which is capable of generating a radical or an acid is mixed in said composition at a ratio of 0.01 to 3 wt. % based on said polysilane and is an organic halogen compound represented by the general formula (2) shown below:

##STR61## wherein Q is bromine atom or chlorine atom;

P is CQ₃, -NH₂, -NHR², -N(R²), -OR² or a substituted or non-substituted phenyl group, wherein Q is as above defined, R² is a phenyl group, naphthyl group or lower alkyl group having not more than 6 carbon atoms; and

R¹ is -CO₃, -NH₂, -NHR², -N(R²)₂, -(CH=CH)_n -W or a substituted or non-substituted phenyl group, wherein Q and R² are as above defined, n is an integer of 1 to 3, W is an aromatic group, heterocyclic group or a group represented by the following general formula (3) ##STR62## wherein Z is an oxygen atom or a sulfur atom; and

R³ is a lower alkyl group or phenyl group.

4. A method of forming a pattern comprising the steps of:

forming a film of an organosilane compound comprising a polysilane having a repeating unit represented by the following general formula (1) on a substrate;

irradiating an actinic radiation onto a predetermined portion of the film of the organosilane compound formed on the substrate; and

removing said predetermined portion of the film irradiated by the actinic radiation by dissolving it with an aqueous alkaline developing solution ##STR63## wherein Ar is a substituted or non-substituted aryl group.

5. The method of forming a pattern according to claim 4, wherein said organosilane compound film further contains a compound which is capable of generating a radical or an acid as it is irradiated by an actinic radiation.

6. The method of forming a pattern according to claim 5, wherein said compound which is capable of generating a radical or an acid is an organic halogen compound represented by the general formula (2) shown below:

##STR64## wherein Q is bromine atom or chlorine atom;

P is --CQ₃, --NH₂, --NHR², --N(R²)₂, --OR² or a substituted or non-substituted phenyl group, wherein Q is as above defined, R² is phenyl group, naphthyl group or lower alkyl group having not more than 6 carbon atoms; and

R¹ is --CQ₃, --NH₂, --NHR², --N(R²)₂, --OR², --(CH=CH)_n --W or a substituted or non-substituted phenyl group, wherein Q and R² are as above defined, n is an integer of 1 to 3, W is an aromatic group, heterocyclic group or a group represented by the following general formula (3) ##STR65## wherein Z is oxygen atom or sulfur atom; and

R³ is lower alkyl group or phenyl group.

7. The method of forming a pattern according to claim 6, wherein said compound which is capable of generating a radical or an acid is mixed in said composition at a ratio of 0.01 to 3 wt. % based on said polysilane.

8. The method of forming a pattern according to claim 4, wherein said organosilane compound film further contains at least one kind of powders selected from SiO₂ powder and SiN powder.

9. The method of forming a pattern according to claim 4, which further comprises a step of heat-drying the organosilane compound film after the developing step thereby to turn the film into a three-dimensional structure.

10. The method of forming a pattern according to claim 9, which further comprises a step of irradiating the entire surface of said organosilane compound film prior to the heat-drying step of the organosilane compound film.

31. The method according to claim 4, wherein the substituted aryl group Ar is substituted by alkyl, fluoroalkyl, bromine, alkoxy, hydroxy or cyano.

11. A method of forming a pattern comprising the steps of:

forming a film of an organosilane compound comprising a polysilane having a repeating unit represented by the following general formula (1) on a substrate;

irradiating an actinic radiation onto a predetermined portion of the film of the organosilane compound formed on the substrate;

heating the film of the organosilane compound after the irradiation of the actinic radiation; and

removing a non-irradiated portion of the film by dissolving it with an organic solvent ##STR66## wherein Ar is a substituted or non-substituted aryl group.

12. The method of forming a pattern according to claim 11, wherein said organosilane compound film further contains a compound which is capable of generating a radical or an acid as it is irradiated by an actinic radiation.

13. The method of forming a pattern according to claim 12, wherein said compound which is capable of generating a radical or an acid is an organic halogen compound represented by the general formula (2) shown below:

##STR67## wherein Q is bromine atom or chlorine atom;

P is --CQ₃, --NH₂, --NHR², --N(R²)₂, --OR² or a substituted or non-substituted phenyl group, wherein is as above defined, R² is phenyl group, naphthyl group or lower alkyl group having not more than 6 carbon atoms; and

R¹ is --CQ₃, --NH₂, --NHR², --N(R²)₂, --OR², --(CH=CH)_n --W or a substituted or non-substituted phenyl group wherein Q and R² are as above defined, n is an integer of 1 to 3, W is an aromatic group, heterocyclic group or a group represented by the following general formula (3) ##STR68## wherein Z is oxygen atom or sulfur atom; and

R³ is lower alkyl group or phenyl group.

14. The method of forming a pattern according to claim 13, wherein said compound which is capable of generating a radical or an acid is mixed in said composition at a ratio of 0.01 to 3 wt. % based on said polysilane.

15. The method of forming a pattern according to claim 11, wherein said organosilane compound film further contains an organometallic compound.

16. The method of forming a pattern according to claim 11, wherein said organosilane compound film further contains at least one kind of powders selected from SiO₂ fine powder and SiN fine powder.

17. The method of forming a pattern according to claim 11, which further comprises a step of heat-drying the organosilane compound film after the developing step thereby to turn the film into a three-dimensional structure.

32. The method according to claim 11, wherein the substituted aryl group Ar is substituted by alkyl, fluoroalkyl, bromine, alkoxy, hydroxy or cyano.

18. A method of forming a pattern comprising the steps of:

forming a film of an organosilane compound comprising a silicon polymer composition comprising a polysilane having a repeating unit represented by the following general formula (1) and a compound which is capable of generating a radical or an acid as it is irradiated by an actinic radiation ##STR69## wherein Ar is a substituted or non-substituted aryl group on a substrate;

irradiating an actinic radiation onto a predetermined portion of the film of the organosilane compound formed on the substrate;

immersing the organosilane compound film irradiated in the preceding step in a solution containing a color component to coloring the organosilane compound film; and

heat-drying the organosilane compound film colored in the preceding step to turn the film into a three-dimensional structure.

19. The method of forming a pattern according to claim 18, wherein said compound which is capable of generating a radical or an acid is an organic halogen compound represented by the general formula (2) shown below:

##STR70## wherein Q is bromine atom or chlorine atom;

P is -CQ₃, -NH₂, -NHR², -N(R²)₂, -OR² or a substituted or non-substituted phenyl group, wherein is as above defined, R² is phenyl group, naphthyl group or lower alkyl group having not more than 6 carbon atoms; and

R¹ is -CQ₃, -NH₂, -NHR², -N(R²)₂, -OR², --(CH=CH)_n -W or a substituted or non-substituted phenyl group, wherein Q and R² are as above defined, n is an integer of 1 to 3, W is an aromatic group, heterocyclic group or a group represented by the following general formula (3) ##STR71## wherein Z is oxygen atom or sulfur atom; and

R³ is lower alkyl group or phenyl group.

20. The method of forming a pattern according to claim 19, wherein said compound which is capable of generating a radical or an acid is mixed in said composition at a ratio of 0.01 to 3 wt. % based on said polysilane.

33. The method according to claim 18, wherein the substituted aryl group Ar is substituted by alkyl, fluoroalkyl, bromine, alkoxy, hydroxy or cyano.

21. A method of forming a pattern comprising the steps of:

forming a film of an organosilane compound comprising a polysilane having a repeating unit represented by the following general formula (4) on a substrate;

irradiating an actinic radiation onto a predetermined portion of the film of the organosilane compound formed;

impregnating at least one kind of powders selected from SiO₂ powder and SiN powder in said predetermined portion irradiated by the actinic radiation; and

heat-drying the film of the organosilane compound after the aforementioned impregnating step thereby to turn the film into a three-dimensional structure ##STR72## wherein R⁴ is a substituted or non-substituted aryl group, or a substituted or non-substituted alkyl group.

34. The method according to claim 21, wherein the substituted aryl group Ar is substituted by alkyl, fluoroalkyl, bromine, alkoxy, hydroxy or cyano.

22. A method of forming an insulating film comprising the steps of:

forming a film of an organosilane compound comprising a polysilane having a repeating unit represented by the following general formula (1) on a substrate; and

heat-drying the film of the organosilane compound in an oxygen-containing atmosphere thereby to turn the film into a three-dimensional structure. ##STR73## wherein Ar is a substituted or non-substituted aryl group.

23. The method of forming an insulating film according to claim 22, wherein said heat-drying is performed at a temperature of 100 to 600°

C.

24. The method of forming an insulating film according to claim 22, which further comprises a step of irradiating the entire surface of said organosilane compound film in an oxygen-containing atmosphere prior to the heat-drying step of the organosilane compound film.

25. The method of forming an insulating film according to claim 24, which further comprises a step of immersing said organosilane compound film in a sol containing an metal alkoxide after the step of irradiating the entire surface of said organosilane compound film, but before said heat-drying step.

26. The method of forming an insulating film according to claim 24, which further comprises a step of impregnating at least either one of SiO₂ fine powder and SiN fine powder in said organosilane compound film after the step of irradiating the entire surface of said organosilane compound film, but before said heat-drying step.

35. The method according to claim 22, wherein the substituted aryl group Ar is substituted by alkyl, fluoroalkyl, bromine, alkoxy, hydroxy or cyano.