Amorphous carbon film, process for forming amorphous carbon film, electrically conductive member and fuel cell bipolar plate having amorphous carbon film
An amorphous carbon film contains carbon as a main component, not more than 30 at. % of hydrogen, not more than 20 at. % of nitrogen and not more than 3 at. % of oxygen (all excluding 0 at. %), and when the total amount of the carbon is taken as 100 at. %, the amount of carbon having an sp 2 hybrid orbital is not less than 70 at. % and less than 100 at. %. Nitrogen and oxygen are concentrated on a surface side of the film and when detected from a surface layer by X-ray photoelectron spectroscopy, oxygen content ratio is not less than 4 at. % and not more than 15 at. % and nitrogen content ratio is not less than 10 at. % and not more than 30 at. %.
1. An amorphous carbon film containing carbon as a main component, not more than 30 at. % of hydrogen, not more than 20 at. % of nitrogen and not more than 3 at. % of oxygen (all excluding 0 at. %), and when the total amount of the carbon is taken as 100 at. %, the amount of carbon having an sp 2 hybrid orbital being not less than 70 at. % and less than 100 at. %,
which is characterized in that nitrogen and oxygen are concentrated on a surface side of the film and when detected from a surface layer within a depth of 2 nm from an outermost surface by X-ray photoelectron spectroscopy, oxygen content ratio is not less than 4 at. % and not more than 15 at. % and nitrogen content ratio is not less than 10 at. % and not more than 30 at. % when the total of the carbon, nitrogen and oxygen of the film surface layer composition is taken as 100 at. %.
2. The amorphous carbon film according to claim 1 , having a dynamic contact angle of not more than 20°.
3. The amorphous carbon film according to claim 1 , wherein nitrogen content ratio detected from the surface layer is not less than 10 at. % and not more than 20 at. %.
4. The amorphous carbon film according to claim 1 , containing not less than 0.5 at. % of oxygen.
5. The amorphous carbon film according to claim 1 , containing not more than 15 at. % of hydrogen.
6. A process for forming the amorphous carbon film according to claim 1 on a surface of a substrate by plasma CVD by introducing reaction gas comprising nitrogen gas and carbon-containing gas including at least one kind of gas selected from gas of a carbon cyclic compound containing carbon having an sp 2 hybrid orbital and gas of a nitrogen-containing heterocyclic compound containing carbon having an sp 2 hybrid orbital and N into a reaction vessel containing the substrate, and generating plasma, which is characterized in that:
the amorphous carbon film is formed by way of a first film forming step, and a second film forming step after the first film forming step, and
the second film forming step is carried out by introducing the reaction gas into the reaction vessel in such a manner that a flow ratio of the nitrogen gas to the carbon-containing gas is greater than the flow ratio in the first film forming step.
7. The process for forming the amorphous carbon film according to claim 6 , wherein the gas flow ratio in the second film forming step is not less than 10.
8. The process for forming the amorphous carbon film according to claim 7 , wherein the gas flow ratio in the second film forming step is not less than 10 and not more than 1000.
9. The process for forming the amorphous carbon film according to claim 6 , wherein flow rate of the reaction gas introduced into the reaction vessel is not less than 100 sccm per m 2 of surface area of a surface to be treated.
10. The process for forming the amorphous carbon film according to claim 6 , wherein the carbon-containing gas includes the gas of the nitrogen-containing heterocyclic compound.
11. The process for forming the amorphous carbon film according to claim 10 , wherein the nitrogen-containing heterocyclic compound is at least one selected from pyridine, pyridine and pyrrole.
12. An electrically conductive member having an amorphous carbon film, which is characterized in comprising a substrate and the amorphous carbon film according to claim 1 formed on at least part of the substrate.
13. A fuel cell bipolar plate, comprising a metal substrate and an amorphous carbon film covering at least part of a surface of the substrate to face an electrode,
which is characterized in that the amorphous carbon film is the amorphous carbon film claim 1 .
14. The amorphous carbon film according to claim 1 , when detected from a surface layer by X-ray photoelectron spectroscopy, the oxygen content ratio is not less than 4 at. % and not more than 11 at. % and the nitrogen content ratio is not less than 12 at. % and not more than 30 at. % when the total of the carbon, nitrogen and oxygen of the film surface layer composition is taken as 100 at. %.
15. The amorphous carbon film according to claim 1 , when detected from a surface layer by X-ray photoelectron spectroscopy, the oxygen content ratio is not less than 5 at. % and not more than 10 at. % and the nitrogen content ratio is not less than 12 at. % and not more than 17 at. % when the total of the carbon, nitrogen and oxygen of the film surface layer composition is taken as 100 at. %.