JP5779988B2 - Corrosion-resistant conductive film, method for producing the same, and corrosion-resistant conductive material - Google Patents

Description

  The present invention relates to a corrosion-resistant conductive film having excellent corrosion resistance or conductivity, a method for producing the same, and a corrosion-resistant conductive material having the corrosion-resistant conductive film on the surface of a substrate (for example, various electrode materials used for separators for fuel cells). .

  As represented by metal separators for polymer electrolyte fuel cells and the like, recently, there has been a demand for a member that can achieve high levels of both corrosion resistance and conductivity.

  However, it is not easy to obtain a corrosion-resistant conductive material that satisfies both of these characteristics. For example, a Ti-based or stainless-based metal material forms a strong and stable passive film on the surface and exhibits excellent corrosion resistance. However, the passive film is made of a stable insulating compound, and usually has a very high resistance and poor conductivity. Under such circumstances, proposals relating to corrosion-resistant conductive materials have been made in the following patent documents.

JP 2000-123850 A JP 2006-524896 A JP 2009-203519 A JP 2011-32507 A

  Patent Document 1 proposes a separator in which a chemically stable noble metal plating layer is provided on a base material made of stainless steel, titanium alloy, or the like. However, the use of such precious metals is expensive. Further, when the amount of noble metal used is reduced, there is a risk of deterioration of adhesion and peeling of the plating layer. Furthermore, when the base material is Al or the like, a local battery is formed at the pinhole portion of the plating layer, and local corrosion such as pitting corrosion may occur on the base material.

  Patent Document 2 proposes that the current collector plate of the fuel cell is made of a bulk solidified amorphous alloy. However, Patent Document 1 describes that the amorphous alloy contains (Zr, Ti) a (Ni, Cu, Fe) b (Be, Al, Si, B) c as a constituent element. There is no mention of any specific characteristics.

  Patent Document 3 proposes an Fe- (Zr, Ti, Hf) oxide layer formed on the surface of an iron-based metal material and having excellent corrosion resistance and conductivity. However, the oxide layer has a contact resistance as high as several tens of ohms to one hundred and several tens of ohms, and is not necessarily excellent in conductivity.

  Patent Document 4 proposes an electrode material for electrolytic generation of ozone water. This electrode material is also made of an alloy of platinum and silver, which are noble metals, and is also expensive.

  The present invention has been made in view of such circumstances, and unlike a conventional film or the like, a corrosion-resistant conductive film exhibiting excellent corrosion resistance or conductivity at a relatively low cost and a method for producing the same. The purpose is to provide. Another object of the present invention is to provide a corrosion-resistant conductive material having the corrosion-resistant conductive film on the substrate surface.

  As a result of intensive studies and trial and error to solve this problem, the present inventor newly found that a film having an amorphous phase composed of Ti-PO exhibits very excellent corrosion resistance and conductivity. . Further, it has been newly found that a film subjected to nitriding treatment exhibits further excellent corrosion resistance and conductivity. The present inventor has developed these results and completed various inventions described below.

《Corrosion-resistant conductive film》
(1) That is, the corrosion-resistant conductive film of the present invention has at least a part of an amorphous phase composed of titanium (Ti), phosphorus (P) and oxygen (O). Simply referred to as “%”), P: 5 to 50%, O: 7 to 50% and Ti: 10 to 80%, and Ti with respect to the sum of the number of Ti atoms and the number of P atoms Ti atomic ratio is the ratio number of atoms of (Ti / Ti + P) is from 0.66 to 0.72, formed on at least a portion of the surface of the substrate, wherein the kite.

(2) The corrosion-resistant conductive film of the present invention exhibits excellent corrosion resistance or conductivity, and does not require a noble metal element, so that it can be formed at a relatively low cost and has very high industrial practicality.

  By the way, it is considered that the corrosion-resistant conductive film of the present invention exhibits excellent corrosion resistance and conductivity because the amorphous phase constituting it is excellent in chemical stability and has large electrical (electron) conductivity. However, it is not always clear why the amorphous phase is excellent in chemical stability and electrical conductivity. The current situation is considered as follows.

  First, since the amorphous phase of the present invention contains Ti and P as constituent elements, it is considered that the electronic phase is similar to the characteristics of metal phosphide. However, little attention has been paid to the corrosion resistance of the amorphous phase composed of Ti and P. This may be because, for example, it is well known that the amorphous phase of Ni—P forms NiO in an oxidizing atmosphere and deteriorates the corrosion resistance.

  On the other hand, the reason for the amorphous phase of the present invention is not clear, but since it is difficult to form phosphate, it is considered that not only conductivity but also excellent corrosion resistance has been developed. Note that the surface of the amorphous phase according to the present invention is smoother than the crystalline material because the surface is homogenized. This point is also considered to be one of the reasons why the corrosion-resistant conductive film of the present invention is superior to the conventional film made of only a crystalline material.

(3) The corrosion resistance and conductivity of the corrosion-resistant conductive film of the present invention can be satisfied simultaneously in a high dimension. However, the corrosion-resistant conductive film of the present invention may be specialized for only one of corrosion resistance or conductivity. For example, the composition or forming method of the film may be changed as appropriate in accordance with the required specifications of the film or member, and either one of the corrosion resistance or conductivity may be enhanced with priority over the other.

(4) It is sufficient that the corrosion-resistant conductive film of the present invention has the above amorphous phase in at least a part thereof. For this reason, the corrosion-resistant conductive film of the present invention may be a mixture of an amorphous phase having an amorphous structure (amorphous phase) and a crystalline phase having a crystalline structure. Further, the constituent elements other than the amorphous phase do not necessarily need to be Ti, P and O as described above. Needless to say, it is more preferable that the entire corrosion-resistant conductive film of the present invention is composed of an amorphous phase.

《Corrosion-resistant conductive material》
(1) The present invention is grasped not only as a corrosion-resistant conductive film but also as a corrosion-resistant conductive material provided with the corrosion-resistant conductive film on the surface of a substrate. That is, the present invention may be a corrosion-resistant conductive material comprising a base material and the corrosion-resistant conductive film of the present invention formed on at least a part of the surface of the base material.

(2) The base material in this specification does not ask | require a material, a shape, a magnitude | size, etc. For example, a member having a predetermined shape may be used, or a material, powder, or the like to be processed or molded from now on. Therefore, the corrosion-resistant conductive material referred to in the present invention can include not only a member having the corrosion-resistant conductive film of the present invention but also a raw material or a raw material (powder or the like).

  Moreover, as long as the corrosion-resistant conductive film of the present invention is formed, the base (core portion) of the base material may be a metal such as Ti, Al, Fe (including stainless steel), Mg, and further, resin, ceramic, etc. But it ’s okay. However, if the base material itself is made of pure titanium, a titanium alloy, stainless steel, or the like, it is easy to obtain a corrosion-resistant conductive material that is more excellent in corrosion resistance.

(3) As an example of the above corrosion-resistant conductive material, for example, there is a separator for a polymer electrolyte fuel cell. That is, the present invention provides a solid polymer electrolyte membrane provided in the center, a fuel electrode provided in contact with one side of the solid polymer electrolyte membrane, and an oxidation provided in contact with the other side of the solid polymer electrolyte membrane. A unit cell comprising an electrode, a fuel electrode and a separator provided outside the oxidation electrode, and a fuel gas is supplied between the separator and the fuel electrode, and the separator and the oxidation electrode In the polymer electrolyte fuel cell in which the oxidant gas is supplied during the period to generate DC power, the separator has the above-described corrosion-resistant conductive film of the present invention on at least a part of its surface. It can also be grasped as a separator for polymer fuel cells.

<< Method for producing corrosion-resistant conductive film >>
The corrosion-resistant conductive film (or corrosion-resistant conductive material) of the present invention can be obtained by the following method according to the present invention, for example, regardless of its formation method or manufacturing method. That is, the corrosion-resistant conductive film (or corrosion-resistant conductive material) of the present invention is preferably obtained by an amorphous phase forming step in which atoms evaporated from a target are deposited on a substrate to form an amorphous phase. That is, by using a physical vapor deposition method (PVD) such as vapor deposition, a corrosion-resistant conductive film having an amorphous phase can be formed relatively easily.

<Others>
(1) The “amorphous phase” referred to in the present specification can be appropriately referred to as an “amorphous layer”.

(2) The corrosion-resistant conductive film of the present invention may contain, in addition to Ti, P or O (further N), a “modified element” that improves the characteristics of the corrosion-resistant conductive film or does not adversely affect it. Moreover, the corrosion-resistant conductive film of the present invention may contain “unavoidable impurities” in addition to the modifying element. Inevitable impurities are elements that are difficult to remove for cost or technical reasons. Such inevitable impurities can be inevitably mixed during the formation of the corrosion-resistant conductive film, as well as when originally included in the supply source of the constituent elements of the amorphous phase. In addition, even if it is an unavoidable impurity when viewed from a certain corrosion-resistant conductive film, it may be a modifying element when viewed from another corrosion-resistant conductive film.

(3) “Corrosion resistance” as used in this specification may be any of acid resistance that does not corrode even in an acidic atmosphere, an oxidizing atmosphere, or a high potential atmosphere, or an oxidation resistance that does not oxidize in a high temperature oxygen atmosphere. This corrosion resistance is indicated by a corrosion rate, an exchange current density, and the like.

  “Conductivity” may be the case where the electrical resistance of the coating itself is small or the contact resistance when it is in contact with another conductive material.

(4) Unless otherwise specified, “x to y” in the present specification includes the lower limit value x and the upper limit value y. Furthermore, a new arbitrary numerical range “ab” can be configured by appropriately combining numerical values described in the present specification and arbitrary numerical values included in “x to y” thereof.

It is a graph which shows the relationship between the atomic ratio of each sample, and an exchange current density. It is sectional drawing which shows 1 cell of a polymer electrolyte fuel cell. It is a disassembled perspective view of 1 cell of a polymer electrolyte fuel cell.

S test piece F polymer electrolyte fuel cell 1 polymer electrolyte membrane 2 fuel electrode 3 oxidation electrode 5 separator

  The present invention will be described in more detail with reference to embodiments of the invention. The contents described in the present specification can be applied not only to the corrosion-resistant conductive film according to the present invention but also to the corrosion-resistant conductive material, the manufacturing method thereof, and the like. One or two or more components arbitrarily selected from the present specification can be added to the above-described components of the present invention. If understood as a product-by-process, the content relating to the manufacturing method can be a component relating to the corrosion-resistant conductive film and the corrosion-resistant conductive material. Note that which embodiment is the best depends on the target, required performance, and the like.

<Amorphous phase>
(1) Composition The corrosion-resistant conductive film of the present invention can exhibit excellent corrosion resistance or conductivity by having an amorphous phase. This amorphous phase contains Ti, P and O (these elements are appropriately referred to as “basic elements”) as essential elements. These composition ranges are not particularly limited. As long as the amorphous phase has the above basic elements, it is considered that excellent corrosion resistance or conductivity can be exhibited in a wide composition range.

  However, when the amorphous phase having Ti, P and O as basic elements (referred to as “Ti—P—O amorphous phase” as appropriate) is 100 atomic% (hereinafter simply referred to as “%”) of the entire amorphous phase, It is preferable that P is 5 to 50%, more preferably 12 to 35%, O is 5 to 50%, more preferably 7 to 30%, and the balance is Ti and inevitable impurities and / or modifying elements. Note that Ti is preferably 10 to 80%, more preferably 20 to 75%. If any of these basic elements is too little or too much, the corrosion resistance or conductivity of the corrosion-resistant conductive film may be lowered.

  In the amorphous phase according to the present invention, in particular, the Ti atomic ratio (Ti / Ti + P), which is the ratio of the number of Ti atoms to the sum of the number of Ti atoms and the number of P atoms, is 0.5 to 0.8, further 0. When it is .66 to 0.72, the corrosion resistance can be further improved while maintaining high conductivity.

  Furthermore, when this amorphous phase contains nitrogen (N) (this amorphous phase is appropriately referred to as “Ti—P—O—N amorphous phase”), the corrosion-resistant conductive film of the present invention is formed from the Ti—P—O amorphous phase. It can exhibit further superior corrosion resistance than the corrosion-resistant conductive film.

  In this tendency, in the amorphous phase, the N atomic ratio (N / Ti + N), which is the ratio of the number of N atoms to the total number of Ti atoms and N atoms, is 0.3 to 0.7, and is further preferably 0.00. This is remarkable when the ratio is 4 to 0.6.

  The amorphous phase of the present invention can contain various modifying elements as described above. Examples of such a modifying element include iron (Fe), nickel (Ni), cobalt (Co), chromium (Cr), vanadium (V), and boron (B).

(2) Structure Since the amorphous phase does not take a clear crystal structure, it is basically homogeneous or isotropic. For this reason, there is almost no crystal grain boundary or lattice defect that becomes a starting point of corrosion, and the corrosion resistance can be improved.

  However, the amorphous phase referred to in the present invention is sufficient as long as strong diffraction is not detected by an X-ray diffractometer (XRD). In other words, the amorphous phase of the present invention may be an amorphous phase that does not have a complete crystal structure, or a latent crystal quality in which weak diffraction is detected by XRD.

  Further, the composition range of the amorphous phase may change in the thickness direction from the outermost layer to the base material. The composition range may vary depending on the region of the amorphous phase.

  The corrosion-resistant conductive film of the present invention can exhibit sufficient corrosion resistance or conductivity simply by covering the surface of the substrate thinly. Specifically, the thickness of the corrosion-resistant conductive film (particularly the thickness of the amorphous phase) may be 10 to 1000 nm, or even 50 to 300 nm.

《Corrosion-resistant conductive film》
The corrosion-resistant conductive film of the present invention has an amorphous phase at least in part and is formed on at least a part of the surface of the substrate. This corrosion-resistant conductive film may be formed by laminating amorphous phases having different compositions. An intermediate layer serving as an underlayer or support layer for the amorphous phase may be provided on the surface of the substrate. In this case, the amorphous phase and intermediate layers thereof can be considered as the corrosion-resistant conductive film of the present invention. An example of the intermediate layer is a Ti ₃ P layer having a crystal structure.

The Ti ₃ P layer itself has conductivity. Further, even if the Ti ₃ P layer is exposed to a corrosive environment for some reason, a Ti—PO film having corrosion resistance is formed on the surface. Therefore, even if the amorphous phase of the present invention is absent or transformed, the corrosion resistance conductivity of the film of the present invention can be ensured. Therefore, when such an intermediate layer is provided in the lower layer of the amorphous phase, the film of the present invention can exhibit more stable corrosion resistance conductivity.

"Production method"
(1) Amorphous phase formation process The formation of the amorphous phase requires the supply of basic elements. The basic element may be supplied from a supply source independent of the base material, or a part of the basic element may be supplied from the base material side. When the basic element is supplied from a source independent of the base material, it is preferable because a corrosion-resistant conductive film having a desired composition can be easily formed on various base materials.

  The method for forming the amorphous phase does not matter. For example, a sputtering method (sputtering), a vapor deposition method (PVD), or a vapor deposition method in a reactive atmosphere (CVD or PVD + CVD) can be used. An appropriate method is selected in consideration of the material / morphology / characteristics of the substrate, the composition of the amorphous phase, the thickness of the corrosion-resistant conductive film, and the like. Among them, a vapor deposition method that can efficiently form a uniform amorphous phase, particularly a physical vapor deposition (PVD) method is preferable.

  PVD is a method in which a basic element of an amorphous phase generated from a deposition material (target) is attached to a substrate surface in a vacuum. For target ablation (evaporation, sublimation, peeling, etc.), resistance heating, electron beam, high frequency induction, laser, or the like can be used.

  A pulse laser deposition (PLD) method may be used in which a target installed in a vacuum chamber is irradiated with laser light from the outside of the chamber, and atoms of basic elements generated from the target are deposited on a substrate. When PLD is used, there is little deviation of component elements from the target amorphous phase, and it is easy to form a corrosion-resistant conductive film having an amorphous phase with a desired composition. In addition, by adjusting the number of (ablation) laser pulses, it is possible to precisely control the deposition rate.

  In addition, a target used in a sputtering method, a vapor deposition method or the like can affect the amorphous phase to be formed, and thus the composition and uniformity of the corrosion-resistant conductive film. When forming a corrosion-resistant conductive film made of an amorphous phase as in the present invention, it is preferable to use a target obtained by a discharge plasma sintering (SPS) method. Incidentally, SPS is a method in which a large amount of pulsed current is applied at a low voltage to the particle gap of the green compact of the raw material powder that is the target, and each particle is sintered by the discharge plasma energy generated instantaneously between the particles. It is.

(2) Nitriding process The introduction of N into the corrosion-resistant conductive film can be performed by nitriding methods such as gas nitriding, ion nitriding, salt bath nitriding. Furthermore, even if nitriding is introduced into the PVD atmosphere, N can be introduced into the corrosion-resistant conductive film.

<Application>
The use of the corrosion-resistant conductive film of the present invention is not particularly limited, and it can be used for various objects. Further, the corrosion-resistant conductive material having the corrosion-resistant conductive film on the base material is not limited to the final product or a form close thereto, but may be a raw material such as an intermediate material or powder. A good example of the corrosion-resistant conductive material is a current-carrying member such as an electrode used in a corrosive environment such as the above-described separator for a polymer electrolyte fuel cell.

The present invention will be described more specifically with reference to examples.
<Production of sample>
(1) A glass substrate (base material) made of alumina silica glass was prepared. A film was formed on these substrates by magnetron sputtering (amorphous phase forming step). Tables 1 and 2 show the atomic ratio of Ti and P constituting the target used at this time (Ti atomic ratio: Ti / Ti + P).

  The target was produced from a mixed powder prepared by variously adjusting the composition of TiP powder (10 to 100 μm) and Ti powder (10 to 100 μm). At this time, the mixed powder was uniformly mixed using a rocking mixer. Note that O contained in the film is supplied by oxygen (oxide) adhering to the particle surface of the raw material powder or oxygen introduced into the sputtering atmosphere. Of course, titanium oxide powder or the like may be used as the O supply source.

  Magnetron sputtering was performed under conditions of 100 W, 1 hour, and 0.5 Pa, using Ar as the sputtering gas and oxygen or nitrogen as the atmosphere adjustment gas.

(2) Further, a part of the samples (Sample Nos. B1 to B6) was subjected to nitriding treatment on the substrate after film formation (nitriding step). This nitriding treatment was performed by placing the test piece in an ammonia gas atmosphere at 850 ° C. for 2 hours.

  In this way, each sample shown in Table 1 and Table 2 formed on the glass substrate was manufactured.

<Observation of film>
(1) For some of the samples shown in Tables 1 and 2, the composition of the film was analyzed by Rutherford backscattering analysis (RBS). The measurement at this time was performed under the conditions of ion species: He, ion energy: 1.8 MeV, scattering angle: 160 °, and vacuum degree of scattering tank: 3 × 10 ⁻⁶ Torr. The results are also shown in Table 1 and Table 2. In addition, the atomic ratios obtained based on the analysis results are also shown in Tables 1 and 2.

(2) The crystal structure of the film of each sample was analyzed with an X-ray diffractometer (XRD). In any case, a sharp peak did not appear, and it was confirmed that each film was amorphous.

(3) The film of any sample showed metallic luster, and the thickness obtained from the step with the glass substrate was about 160 nm.

<< Corrosion resistance and conductivity >>
(1) The exchange current density of each film formed on the glass substrate was measured. Specifically, the anodic polarization of a gentle sample (film) in an aqueous solution (1NH ₂ SO ₄ : pH˜0) of sulfuric acid (H ₂ SO ₄ ) at 1 normality (H: 1 mol / L) was measured. The sweep rate at this time was 50 mV / min, and a saturated silver chloride electrode (SSE: Ag / AgCl / saturated KCl aqueous solution) was used as a reference electrode. The results thus obtained are also shown in Tables 1 and 2. In all the samples, the current density was stable even when the applied voltage was increased.

(2) The volume resistivity of the film of each sample was measured by the four probe method. In all cases, the volume resistivity was 1 to 10 (× 10 ⁻⁶ Ω · m).

<Evaluation>
Based on Tables 1 and 2, the relationship between the Ti atomic ratio (Ti / Ti + P) in each film and the exchange current density is shown in FIG. As is apparent from Tables 1 and 2 and FIG. 1, it can be seen that all the samples exhibit excellent corrosion resistance and conductivity.

  In particular, in the case of a sample not subjected to nitriding treatment (Ti-PO amorphous phase), when the Ti atomic ratio in the film (amorphous phase) is 0.66 to 0.75, the exchange current density rapidly decreases. It was found that it exhibited very high corrosion resistance. From Table 1, the Ti atomic ratio in this film was almost the same as the Ti atomic ratio in the target.

  In the case of the sample subjected to nitriding treatment (Ti—P—O—N amorphous phase), the exchange current density proportional to the corrosion rate was further reduced, and further excellent corrosion resistance was exhibited. It was also found that this corrosion resistance tends to improve with the increase in the atomic ratio. Moreover, even when the N atomic ratio (N / Ti + N) in the film changes in a wide range of 0.05 to 0.6, the corrosion resistance is stable. Incidentally, from Table 2, when N was introduced into the film, the Ti atomic ratio in the film was about 5 to 10% lower than the Ti atomic ratio in the target.

《Polymer fuel cell》
As one embodiment of the corrosion-resistant conductive film or corrosion-resistant conductive material according to the present invention, a solid polymer fuel cell comprising a solid polymer fuel cell separator having a corrosion-resistant conductive film formed on the surface of a titanium substrate is shown in FIG. Shown in FIG. 2B.

  The solid polymer fuel cell utilizes the fact that a solid polymer electrolyte membrane having a proton exchange group in the molecule functions as a proton conductive electrolyte. Specifically, as shown in FIGS. 2A and 2B, in the polymer electrolyte fuel cell F, the oxidation electrode 2 and the fuel electrode 3 are joined to both sides of the solid polymer electrolyte membrane 1, respectively. Further, a separator 5 is disposed outside the electrodes via a gasket 4. The separator 5 on the oxidation electrode 2 side is provided with an air supply port 6 and an air discharge port 7, and the separator 5 on the fuel electrode 3 side is provided with a hydrogen supply port 8 and a hydrogen discharge port 9.

  In the separator 5, a plurality of grooves 10 extending in the flow direction of the hydrogen g and the air o are formed for conduction and uniform distribution of the hydrogen g and the air o. Further, the cooling water w fed from the water supply port 11 circulates inside the separator 5 and is then discharged from the drain port 12. The water cooling mechanism built in the separator 5 suppresses overheating of the solid polymer electrolyte membrane and the like due to heat generated during power generation.

  Hydrogen g sent from the hydrogen supply port 8 into the gap between the fuel electrode 3 and the separator 5 becomes protons that have released electrons, passes through the solid polymer electrolyte membrane 1, and passes through the gap between the oxidation electrode 2 and the separator 5. It reacts with oxygen in the passing air o and burns. Then, electric power can be supplied to the load between the oxidation electrode 2 and the fuel electrode 3.

  In general, a fuel cell has a very small amount of power generation per cell. For this reason, a desired output (amount of electric power) is ensured by stacking a plurality of cells with one unit between the pair of separators 5 and 5. However, when a large number of cells are stacked, the contact resistance between the separator 5 and the electrodes 2 and 3 is increased, the power loss is also increased, and the power generation efficiency of the polymer electrolyte fuel cell F is likely to be lowered.

Here, since the separator 5 of the present example has a corrosion-resistant conductive film having excellent conductivity on the surface layer, the contact resistance between the oxidation electrode 2 and the fuel electrode 3 is reduced while ensuring the corrosion resistance. The Therefore, by using the corrosion-resistant conductive material according to the present embodiment, it is possible to easily obtain a separator for a polymer electrolyte fuel cell that is excellent in workability, impact resistance, and the like and that achieves both corrosion resistance and conductivity.

Claims (8)

Having at least part of an amorphous phase composed of titanium (Ti), phosphorus (P) and oxygen (O);
When the entire amorphous phase is 100 atomic% (simply referred to as “%”), P is 5 to 50%, O is 7 to 50%, and Ti is 10 to 80%. Ti atomic ratio (Ti / Ti + P) which is a ratio of the number of Ti atoms to the sum of the number and the number of P atoms is 0.66 to 0.72.
Corrosion conductive film, wherein the kite is formed on at least a portion of the surface of the substrate.   2. The corrosion-resistant conductive film according to claim 1, wherein the amorphous phase is P: 12 to 35%, O: 8 to 30%, and Ti: 20 to 75% when the whole is taken as 100%.   The corrosion-resistant conductive film according to claim 1 or 2, wherein the amorphous phase has a Ti atomic ratio (Ti / Ti + P) of 0.67 to 0.71.   The corrosion-resistant conductive film according to claim 1, wherein the amorphous phase further contains nitrogen (N).   5. The N phase ratio (N / Ti + N), which is a ratio of the number of N atoms to the total number of Ti atoms and N atoms, is 0.3 to 0.7 in the amorphous phase. Corrosion-resistant conductive film. Having an amorphous phase forming step of forming an amorphous phase by attaching atoms evaporated from a target onto a substrate;
A method for producing a corrosion-resistant conductive film, comprising forming the corrosion-resistant conductive film according to claim 1 on the substrate.   Furthermore, the manufacturing method of the corrosion-resistant conductive film of Claim 6 provided with the nitriding process which nitrides the said corrosion-resistant conductive film. A substrate;
The corrosion-resistant conductive film according to any one of claims 1 to 5, formed on at least a part of the surface of the substrate,
A corrosion-resistant conductive material characterized by comprising:

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