Method of manufacturing semiconductor device, method of forming pattern film, and metal-containing organic film

1. A method of manufacturing a semiconductor device, comprising:

forming an organic film containing polyacrylonitrile on a target film on a semiconductor substrate;

applying a metal compound to the organic film to form a composite film;

removing the composite film partially to form a pattern;

heating the pattern-formed composite film; and

processing the target film by using the heated composite film as a mask.

2. The method of manufacturing the semiconductor device according to claim 1 , wherein

a temperature in the heating is 200° C. or more and less than 1000° C.

3. The method of manufacturing the semiconductor device according to claim 1 , wherein

a temperature in the heating is 200° C. or more and less than 600° C.

4. The method of manufacturing the semiconductor device according to claim 1 , further comprising:

before the heating, embedding a core material in a portion from which the composite film is removed in the forming the pattern and after the heating, removing the core material.

5. The method of manufacturing the semiconductor device according to claim 1 , wherein

the composite film is formed by applying a precursor of the metal compound to the organic film, and applying an oxidant to the organic film including the precursor.

6. The method of manufacturing the semiconductor device according to claim 5 , wherein

the a precursor of the metal compound includes at least one selected from the group consisting of AlCl 3 , TiCl 4 , WCl 6 , VCl 4 , HfCl 4 , ZrCl 4 and trimethylaluminum.

7. The method of manufacturing the semiconductor device according to claim 1 , wherein

the heated composite film contains a structure in which a cyano group of polyacrylonitrile is cyclized and a metal compound is coordinated to a nitrogen atom of the cyclized cyano group.

8. The method of manufacturing the semiconductor device according to claim 1 , wherein

the heated composite film contains a structure represented by the following chemical formula (P3),

wherein MX represents a metal compound, m/2 represents an integer of two or more, and . . . represents a coordinate bond.

9. The method of manufacturing the semiconductor device according to claim 1 , wherein the removing of the composite film partially is performed by etching.

10. The method of manufacturing the semiconductor device according to claim 1 , wherein the organic film is produced by use of organic solvent and polymer containing acrylonitrile.

11. The method of manufacturing the semiconductor device according to claim 1 , wherein a content ratio of acrylonitrile to polyacrylonitrile in the organic film is 90 to 100 mol %.

12. A method of forming a pattern film, comprising:

forming an organic film containing polyacrylonitrile;

applying a metal compound to the organic film to form a composite film;

removing the composite film partially to form a pattern; and

heating the pattern-formed composite film.

13. The method of forming the pattern film according to claim 12 , wherein a temperature in the heating is 200° C. or more and less than 1000° C.

14. The method of forming the pattern film according to claim 12 , wherein

a temperature in the heating is 200° C. or more and less than 600° C.

15. The method of forming the pattern film according to claim 12 , further comprising:

before the heating, embedding a core material in a portion from which the composite film is removed in the forming the pattern and after the heating, removing the core material.

16. The method of forming the pattern film according to claim 12 , wherein

the composite film is formed by applying a precursor of the metal compound to the organic film, and applying an oxidant to the organic film including the precursor.

17. The method of forming the pattern film according to claim 16 , wherein

the a precursor of the metal compound includes at least one selected from the group consisting of AlCl 3 , TiCl 4 , WCl 6 , VCl 4 , HfCl 4 , ZrCl 4 and trimethylaluminum.

18. The method of forming the pattern film according to claim 12 , wherein

the heated composite film contains a structure in which a cyano group of polyacrylonitrile is cyclized and a metal compound is coordinated to a nitrogen atom of the cyclized cyano group.

19. The method of forming the pattern film according to claim 12 , wherein

the heated composite film contains a structure represented by the following chemical formula (P3),

wherein MX represents a metal compound, m/2 represents an integer of two or more, and . . . represents a coordination bond.

20. The method of forming a pattern film according to claim 12 , wherein the removing of the composite film partially is performed by etching.

21. The method of forming a pattern film according to claim 12 , wherein the organic film is produced by use of organic solvent and polymer containing acrylonitrile.

22. The method of forming a pattern film according to claim 12 , wherein a content ratio of acrylonitrile to polyacrylonitrile in the organic film is 90 to 100 mol %.

23. A metal-containing organic film containing a structure in which a cyano group of polyacrylonitrile is cyclized and a metal compound is coordinated to a nitrogen atom of the cyclized cyano group.

24. The metal-containing organic film according to claim 23 , containing a structure represented by the following chemical formula (P3),

wherein MX represents a metal compound, m/2 represents an integer of two or more, and . . . represents a coordinate bond.

25. The metal-containing organic film according to claim 24 , wherein

m/2 in the chemical formula (P3) is 10 or more.