WO2019065225A1 - Method for manufacturing hard carbon-based coating, and coated member - Google Patents

Abstract

A method for making a hard carbon coating comprising: step A for preparing a coating forming apparatus having a power source device and a discharge electrode containing a carbon material, and preparing a substrate comprising a surface on which the coating is to be formed; and step B for using the coating forming apparatus to effect repeated discharge between the discharge electrode and the substrate in a prescribed coating forming atmosphere, thereby forming a hard carbon coating on the surface. Step B is carried out under conditions such that the coating-forming atmosphere and / or the discharge electrode contain at least one of hydrogen atoms, oxygen atoms, water and carbon dioxide molecules.

Description

Method of producing hard carbon-based film, and coated member

The present disclosure relates to a method of producing a hard carbon-based coating, and a coated member.
This application claims priority based on Japanese Patent Application No. 2017-185027 filed on Sep. 26, 2017, and uses the entire contents described in the Japanese application.

Diamond, diamond like carbon (DLC), carbon nanotube (CNT), or fullerene as a coating material on the tool surface, sliding component surface, corrosion resistant component surface, acid / alkali resistant component surface, or electrode material surface, etc. A coating of a carbon material including (C ₆₀ , C ₇₀ , C _{74 and the} like) and the like is used.

Generally as a manufacturing method of a film, the film-forming methods, such as chemical vapor deposition (Chemical Vapor Deposition: CVD) and physical vapor deposition (Physical Vapor Deposition: PVD), are used.

On the other hand, as in Patent Document 1, there is known a technique for repairing a crack, a scratch, or a worn portion of a tool surface by electric discharge. The principle is that the energy of discharge discharges a metal, which is one of the electrodes, in a flash, and draws it into a substrate (tool or part) facing the other, and forms and deposits the film. This method is known as a method for forming a coating of a high melting point metal or the like.

Unexamined-Japanese-Patent No. 2010-132951

The method for producing the hard carbon-based coating of the present disclosure is
A film forming apparatus having a power supply device and a discharge electrode containing a carbon material, and a step A of preparing a substrate having a surface on which a film is to be formed,
A step B of forming a hard carbon-based film on the surface by repeatedly generating a discharge between the discharge electrode and the base material under a predetermined film forming atmosphere by the film forming apparatus;
The process B is
The deposition is performed under the condition that at least one of the film forming atmosphere and the discharge electrode contains at least one of a hydrogen atom, an oxygen atom, a water molecule, and a carbon dioxide molecule.

The coated member of the present disclosure is
A coated member comprising a substrate and a hard carbon-based film formed on at least a part of the substrate,
The hard carbon-based film contains at least one of a hydrogen atom and an oxygen atom,
A coated member, wherein X being a peak position in Raman spectroscopy of the hard carbon-based coating and W being a half width at the peak position satisfy the following conditions.
38 cm ^-1 <W <500 cm ^-1
16 × (X-1347.5) +39 <W <16 × (X-1335) +39
X <1370 cm ^-1

The coated member of the present disclosure is
A coated member comprising a substrate and a hard carbon-based film formed on at least a part of the substrate,
The hard carbon-based film contains at least one of a hydrogen atom and an oxygen atom,
D / G which is a ratio of the peak intensity of D band to the peak intensity of G band in Raman spectroscopy of the hard carbon-based film, and W which is the half width of the D band,
W ≦ 115 cm ⁻¹ , and D / G <9.0 and 80 / (D / G) ^0.5 <W <180 / (D / G) ^0.5 or 115 cm ⁻¹ <W <500 cm ⁻¹ And D / G <2.8, or W <50 cm ⁻¹ , and 10.5 <D / G are satisfied.

The coated member of the present disclosure is
A coated member comprising a substrate and a hard carbon-based film formed on at least a part of the substrate,
The hard carbon-based film includes at least one of a hydrogen atom and an oxygen atom, and a site having a peak of D band and a peak of G band in Raman spectroscopy,
Furthermore, the peak position in Raman spectroscopy is a site at 910 ± 50 cm ⁻¹ ,
The peak position in Raman spectroscopy is a site at 810 ± 30 cm ⁻¹ ,
The site where the peak position is 705 ± 30 cm ⁻¹ in Raman spectroscopy,
The peak position in Raman spectroscopy is a site at 535 ± 30 cm ⁻¹ ,
The peak position in Raman spectroscopy is a site of 260 ± 20 cm ⁻¹ ,
The site of peak position at 210 ± 20 cm ⁻¹ in Raman spectroscopy,
The site of the peak position 135 ± 20 cm ⁻¹ in Raman spectroscopy,
It includes at least one of a site with a peak position of 95 ± 10 cm ⁻¹ in Raman spectroscopy and a site with a peak position of 2327 ± 10 cm ⁻¹ in Raman spectroscopy.

The coated member of the present disclosure is
A coated member comprising a substrate and a hard carbon-based film formed on at least a part of the substrate,
The hard carbon coating is hydrogen atom, and at least one of an oxygen atom, and the peak position in the Raman spectroscopy at 1335cm ^-1 or 1349cm ^-1 or less, the half width at the peak position is 30 cm ^-1 or more 95cm ^{- 1} part or less,
Peak position in the Raman spectroscopy at 1349cm ^-1 or 1370 cm ^-1 or less, a half value width 95cm ^-1 or 350 cm ^-1 or less site at the peak position, and the peak position is 1300 cm ^-1 or more in the Raman spectroscopy 1335Cm ^-1 In the following, the full width at half maximum at the peak position includes at least one of ¹ cm ⁻¹ or more and 29 cm ⁻¹ or less.

It is explanatory drawing which shows the manufacturing method of a hard carbon type film using a 1st film-forming apparatus. It is explanatory drawing which shows the manufacturing method of a hard carbon-type film using the 2nd film-forming apparatus. It is explanatory drawing which shows the manufacturing method of a hard carbon-type film using the 3rd film-forming apparatus. It is a cross-sectional schematic diagram of the member with a film in which the hard carbon-type film was formed on the base material. It is a graph which shows the relationship between the peak position of D band of each sample of test 2, and the half value width in the peak position. It is a graph which shows the relationship between D / G ratio of each sample of test 2, and the half value width in D band.

[Problems to be solved by the present disclosure]
The conventional hard carbon-based film formation requires special equipment for performing CVD, PVD or the like, and the cost and time required for film formation make it desirable to have a simpler method. The method of Patent Document 1 forms a film by discharging the same metal material as a tool or a base of a part by discharge, and has not been attempted as a film of a carbon-based material (a material in which carbon is a mainstream).

When considering the formation of a hard carbon-based film, it is a relatively soft carbon electrode that is used. The term "soft" as used herein means that the bond is weak and that the hardness is physically low. The carbon electrode is a highly conductive SP2 bond, an electrode rich in SP2-like bonds, or an electrode rich in π bonds. Therefore, the film formed on the substrate is also a film having many SP2 bonds, SP2-like bonds, and π bonds. In many applications, including tools, it is an important property that the coating be hard. Here, the SP2-like bond is a bond in which the peak position is similar to that of the SP2 bond and the half width of the peak position is larger than that of the SP2 bond in the spectrum obtained by Raman spectroscopy. The half-width of the ordered SP2 bond is as small as less than 20 cm ^-1 , but the half-width becomes larger as the bond order gets disordered. Even a bond with a half width greater than SP2 bond is referred to herein as SP2 like bond because its physical properties are similar to SP2 bond.

Therefore, an object of the present disclosure is to provide a method for producing a hard carbon-based film that can easily form a hard carbon-based film. Another object of the present disclosure is to provide a coated member in which a hard carbon-based coating is formed on a substrate.

[Effect of the present disclosure]
According to the method of producing a hard carbon-based film, a hard film can be easily formed.

The said member with a film is equipped with a harder carbon-based film than before.

Embodiments of the Present Disclosure
The contents of the embodiment of the present disclosure will be listed and described.

As the bond of carbon atoms, SP2 bond, SP2 like bond, π bond, SP3 bond, or SP3 like bond is present. Here, the SP2-like bond is a bond showing physical properties similar to the SP2 bond, and the SP3-like bond is a bond showing physical properties similar to the SP3 bond. These bonds can be distinguished by the peak position of the spectrum obtained by Raman spectroscopy or the full width at half maximum (full width at half maximum) between the peak position and the peak position, as described later. SP2 bonds and SP2 like bonds are found in relatively soft carbon materials such as graphite. In addition, π bonds are also found in relatively soft carbon materials. On the other hand, SP3 bonds and SP3 like bonds are found in hard carbon materials such as diamond. Further, as the flat SP2 bond or the SP2-like bond is curved in a curved shape, the SP3 bond or a bond approaching the SP3-like bond is also recognized in a relatively hard carbon material. The SP2 bond or a bond in which the SP2 like bond is curved like a curved surface includes, for example, a bond forming a bond loop in a minute region such as a carbon nanotube or a fullerene. Such carbon bonds are not planar like SP2 bonds and can be said to be SPx bonds (2 <x <3) or SPx-like bonds (2 <x <3). If the carbon bond of the hard carbon-based film is removed from the SP2 bond, the ratio of π bond of the hard carbon-based film also decreases and the hard carbon-based film becomes hard.

As described above, if the ratio of SP3 bond, SP3-like bond, SPx bond, and SPx-like bond of carbon atoms in the carbon-based film is large, it becomes a hard carbon-based film. The inventors of the present application diligently studied a method capable of forming such a hard carbon-based film easily and efficiently. As a result, at least SP3 bond, SP3 like bond, SPx bond, and SPx like bond by repeatedly performing discharge using a highly conductive carbon electrode having a large proportion of SP2, SP2, and π bonds. It was conceived to form a hard carbon-based film containing one. Below, the manufacturing method of a hard carbon type film, and the detail of a member with a film which has a hard carbon type film are explained.

(1) The method for producing a hard carbon-based film according to the embodiment
A film forming apparatus having a power supply device and a discharge electrode containing a carbon material, and a step A of preparing a substrate having a surface on which a film is to be formed,
A step B of forming a hard carbon-based film on the surface by repeatedly generating a discharge between the discharge electrode and the base material under a predetermined film forming atmosphere by the film forming apparatus;
The process B is
The deposition is performed under the condition that at least one of the film forming atmosphere and the discharge electrode contains at least one of a hydrogen atom, an oxygen atom, a water molecule, and a carbon dioxide molecule.

According to the above method for producing a hard carbon-based film, the hard carbon-based film is formed on the surface of the substrate by a simple operation of repeatedly generating a discharge between the conductive discharge electrode containing the carbon material and the substrate. It can be formed. In addition, since an inexpensive and easily available material such as graphite can be used as the conductive carbon material, the productivity of the hard carbon-based film is excellent also in that respect.

Here, the hard carbon-based film is a hard film containing carbon as a main component or a hard film containing carbon as a minor component. The film containing carbon as a main component is a film in which the content of carbon in the film is 50 atomic% or more. The film containing carbon as a secondary component is a film having a carbon content of more than 10 atomic% and less than 50 atomic%. The hard coating means that carbon contained in the coating has at least one of SP3 bond, SP3 like bond, SPx bond (2 <x <3), and SPx like bond (2 <x <3). Is the coating that

The hard coating is, for example, a coating satisfying the measurement results of Raman spectroscopy defined in the item of the coated member described later. More specifically, examples of the hard carbon-based film include films composed of 100% carbon diamond, tetrahedral amorphous carbon, carbon nanotubes, and the like. In addition, carbon-based coatings with less than 100% carbon, such as coatings of carbon nitride (CN) or carbon boronitride (BCN), are also included as one of the hard carbon-based coatings. Furthermore, a film containing a fibrous carbon material (including carbon nanotubes and the like) having high tensile strength or a conductive carbon material (including a portion of SP2 bonding, a portion of SP2 like bonding, a fullerene and the like) is also disclosed. Included in the disclosed hard carbon-based coatings. The hard carbon-based film containing the fibrous carbon material has an effect of improving the flexural strength of the member on which the hard carbon-based film is formed. In addition, the conductive carbon material contained in the hard carbon-based coating can function as a lubricant. Such a hard carbon-based film can be used as a film formed on a tool, a mold, a sliding member, a corrosion resistant member, an electrode member or the like.

As described in the above manufacturing method, by including at least one of a hydrogen atom, an oxygen atom, a water molecule, and a carbon dioxide molecule in a film formation atmosphere, the formation suppression of SP2 bond, SP2 like bond, and π bond or It can be removed. As a result, the ratio of SP3 bond, SP3 like bond, SPx bond, and SPx like bond in the hard carbon-based coating can be increased.

Further, as described in the above production method, by including at least one of a hydrogen atom, an oxygen atom, a water molecule, and a carbon dioxide molecule in the discharge electrode, the formation of SP2 bond, SP2 like bond, and π bond is suppressed. Or it can be removed. As a result, the ratio of SP3 bond, SP3 like bond, SPx bond, and SPx like bond in the hard carbon-based coating can be increased.

(2) As one mode of the manufacturing method of the hard carbon system film concerning an embodiment,
An embodiment in which the deposition atmosphere is atmospheric pressure can be mentioned.

When the deposition atmosphere is atmospheric pressure, the configuration of the deposition apparatus can be simplified. Therefore, the hard carbon-based film can be formed by a simple method.

(3) As one mode of the manufacturing method of the hard carbon system coating concerning the embodiment,
The form in which the said film-forming atmosphere is water can be mentioned.

In order to increase the proportion of SP3 bonds and SPx bonds in hard carbon-based coatings, it is important to freeze bonds in high energy states faster, as described later. Therefore, it is preferable to cool the substrate with a heat sink or to discharge the substrate in water or in liquid nitrogen or the like. It is easiest to discharge in water, and a hard carbon-based coating can be formed with good productivity.

(4) As one mode of a method of manufacturing a hard carbon-based film according to the embodiment,
The power supply device is an alternating current power supply,
The form which the alternating voltage applied to the said discharge electrode is 3.6 kV or more can be mentioned.

By using the power supply device as an AC power supply, it is possible to repeat that the discharge occurs when the voltage of the discharge electrode is increased. A negative bias potential may be applied to the substrate side. The bias potential may be a self bias potential or a bias potential externally applied to the substrate. In addition, the discharge electrode may be vibrated to urge the discharge to occur periodically.

As a result of the study of the present inventors, it has been found that it is important to efficiently give a large energy which could not be considered in the past in a quick and efficient manner and to freeze the bond of high energy states faster in repetitive discharge. The Therefore, in the above configuration, a high AC voltage of 3.6 kV or more is applied to the discharge electrode. Such voltages provide more energy between the electrode and the substrate than conventional techniques for forming a metallic material, such as a tungsten film, on the substrate. With such a voltage, it is possible to convert the constituent material of the carbon electrode having a large proportion of SP2 bonds and SP2-like bonds into a hard carbon-based film having a large ratio of SP3 bonds and SP3-like bonds.

(5) As one mode of the manufacturing method of the hard carbon system film concerning the embodiment,
The power supply device is a DC power supply,
The DC voltage applied to the discharge electrode is 3.6 kV or more,
The discharge electrode is periodically oscillated to produce a discharge having a pulse width of less than 100 milliseconds.

By applying a high DC voltage of 3.6 kV or more to the discharge electrode, the constituent material of the carbon electrode having a large proportion of SP2 bond and SP2 like bond as in the above (4), SP3 bond and SP3 like bond It can be converted to a hard carbon-based film having a high proportion of Further, by causing the discharge electrode to vibrate with respect to the substrate, the discharge can be continuously maintained, and a wide continuous carbon-based coating can be formed. Also in this configuration, a negative bias potential may be applied to the substrate side.

(6) As one mode of a method of manufacturing a hard carbon-based film according to the embodiment,
The film forming apparatus includes a charging circuit that stores power from the power supply device.
A discharge circuit for discharging the power of the charging circuit in a pulse shape;
A discharge between the discharge electrode and the substrate with a voltage greater than 125 V and a pulse width less than 1 millisecond, or a voltage between the discharge electrode and the substrate with a voltage greater than 50 V and a pulse width less than 10 microseconds And a discharge control unit configured to control the discharge circuit to generate the discharge.

As shown in the above configuration, by applying a predetermined or higher voltage between the discharge electrode and the base material in an extremely short time, as in the above (4) and (5), SP2 coupling and SP2 The constituent material of the carbon electrode having a large proportion of similar bonds can be converted into a hard carbon-based film having a large proportion of SP3 bonds and SP3-like bonds. Also in this configuration, the discharge electrode may be vibrated or a negative bias potential may be applied to the substrate side.

(7) As one mode of the manufacturing method of the hard carbon system coating concerning an embodiment,
The base material may be in the form of a cemented carbide, an iron-based material, a boronitride-based material, a cubic boron nitride-based material, a cermet, a Ni-based material, or a conductive ceramic.

The materials listed in (7) above are mainly constituent materials of the tool. Therefore, according to the above-mentioned composition, a tool (member with a film) which has a hard carbon system film can be produced.

(8) As one mode of a method of manufacturing a hard carbon-based film according to the embodiment,
The said discharge electrode can mention the form which is a carbon material containing 90 mass% or more of carbon atoms.

By containing 90 mass% or more of carbon atoms in the discharge electrode, a hard carbon-based film is easily formed, and the ratio of SP3 bond and SP3-like bond in the hard carbon film can be increased. In a low purity carbon electrode containing a large amount of a binder for solidifying a carbon material, it is difficult to form a hard carbon-based film having SP3 bond and SP3 like bond. It is preferable to make content of a carbon atom into 95 mass% or more. The more preferred content of carbon atoms is 98% by mass or more. Furthermore, among the elements other than carbon, the covalent bondable element is preferably 50% by mass or more. Furthermore, it is preferable that the carbon-based material of the discharge electrode has the features of the hard carbon-based film of the present disclosure. By doing so, it is because it can be converted to a harder carbon structure by the method of manufacturing a hard carbon-based film according to the embodiment. By the other methods such as the sputtering method, only the carbon film of the conventional structure can be formed regardless of the raw material target.

(9) As one mode of a method of manufacturing a hard carbon-based film according to the embodiment,
The said discharge electrode can mention the form which contains 90 mass% or more of a carbon atom, a boron atom, and a nitrogen atom in total.

By including a boron atom in addition to the carbon atom to the discharge electrode, a hard carbon-based film containing boride carbon as a main component can be formed. By including nitrogen atoms in addition to carbon atoms in the discharge electrode, a hard carbon-based film containing carbon nitride as a main component can be formed. By including a boron atom and a nitrogen atom in addition to the carbon atom in the discharge electrode, a hard carbon-based film containing carbon as its main component can be formed.

(10) The coated member according to the embodiment is
A coated member comprising a substrate and a hard carbon-based film formed on at least a part of the substrate,
The hard carbon-based film contains at least one of a hydrogen atom and an oxygen atom,
The peak position X in Raman spectroscopy of the hard carbon coating and the half width W at the peak position satisfy the following conditions.
38 cm ^-1 <W <500 cm ^-1
16 × (X-1347.5) +39 <W <16 × (X-1335) +39
X <1370 cm ^-1

In the spectrum obtained by Raman spectroscopy using a laser excitation wavelength of 532 nm, SP3 bond forms a sharp peak at a position of less than 1325cm ^-1 or 1335cm ^-1 (half-value width of less than 20 cm ^-1). When SP3 bonds of order is disturbed come, the peak position is less than 1335cm ^-1 or 1400 cm ^-1, consisting also half width larger (20 cm ^-1 or higher). In the present specification, a peak is shifted to a position adjacent to the peak of SP3 binding, and the binding having a larger half width is referred to as SP3-like binding. Here, in the case specific, peak positions even less 1335Cm ^-1 or 1400 cm ^-1, the half width is small (less than 20 cm ^-1) which may be bonded of the carbon material obtained. This is an SP3-like bond while the order of the SP3 bond is improved, and is included in the SP3-like bond of the present disclosure. This unique SP3-like bond is suitable as a coating of a tool because it contributes to the improvement of the hardness of the hard carbon-based coating. On the other hand, in the spectrum obtained by Raman spectroscopy, the half-value width to form a peak of less than 20 cm ^-1 SP2 bonds to the position of less than 1500 cm ^-1 or 1650 cm ^-1. When SP2 bonds of order is disturbed come, the peak position does not change (1500 cm less than ^-1 or 1650 cm ^-1), the half width increases with 20 cm ^-1 or more. In the present specification, a bond having a larger half width with respect to SP2 bond is referred to as SP2-like bond. In view of the definition of each of these bonds, if the result of measurement of the hard carbon-based film by Raman spectroscopy satisfies the range described in (7) above, at least SP3 bond and SP3-like bond in the hard carbon film. It can be determined that one is formed. The lower limit value of X is preferably 1335 cm ⁻¹ .

(11) The member with a film according to the embodiment is
A coated member comprising a substrate and a hard carbon-based film formed on at least a part of the substrate,
The hard carbon-based film contains at least one of a hydrogen atom and an oxygen atom,
D / G which is a ratio of the peak intensity of D band to the peak intensity of G band in Raman spectroscopy of the hard carbon-based film, and W which is the half width of the D band,
W <50 cm ⁻¹ , and D / G> 10.5, or W ≦ 115 cm ⁻¹ , and D / G <9.0 and 80 / (D / G) ^0.5 <W <180 / (D / G) ^0.5 or 115 cm ⁻¹ <W <500 cm ⁻¹ and D / G <2.8 are satisfied.

In general, D band peak formed near 1360 cm ^-1 in Raman spectroscopy, but refers to a peak formed near 1580 cm ^-1 and G bands, in this specification, is formed below 1325Cm ^-1 or 1400 cm ^-1 The peak that is formed is called D band, and the peak formed at 1500 cm ⁻¹ or more and less than 1650 cm ⁻¹ is called G band. That is, the D band corresponds to SP3 binding and SP3 like binding, and the G band corresponds to SP2 binding and SP2 like binding. Therefore, if the peak intensity ratio D / G of both bands and the half width W in the D band satisfy the above ranges, it can be determined that SP3 bond and SP3 like bond are formed in the hard carbon-based film. . The high D / G indicates that there are many SP3 bonds and SP3 like bonds in the hard carbon-based film, so the lower limit of D / G is preferably 1.0 or more, and 1.5 It is more preferable that it is the above, and it is more preferable that it is 2.0 or more. In specific cases, even less than the peak position 1335Cm ^-1 or 1400 cm ^-1, the half width is small (less than 20cm ^-1), D / G is sometimes obtained binding of 100 or more carbon materials. This is an SP3-like bond while the order of the SP3 bond is improved, and is included in the SP3-like bond of the present disclosure. This unique SP3-like bond is suitable as a coating of a tool because it contributes to the improvement of the hardness of the hard carbon-based coating. However, if the hard carbon-based film contains 10% or more of the area having the area of the lower limit or more, the remaining D / G of 0.2 or more is sufficient. If the hard portion is contained in the hard carbon-based film by 10% or more, the hard portion causes percolation in the film. Therefore, the hard carbon-based coating is supported by the hard portion contained in the coating and becomes hard to wear. Here, it is possible to use a color-coded Raman image or a Raman image displayed in black and white contrast to judge the area ratio. About four levels of gradation of the Raman image are appropriate. In the creation of a Raman image, it is preferable that image processing of five or more gradation images in which the intensity of the peak is reflected from the spectrum obtained by Raman spectroscopy be about four. The peak position of the spectrum can be accurately determined by subtracting the background from the spectrum and fitting with a Gaussian distribution. The background is determined, for example, as follows. First, the part (temporary peak) which shows local maximum from a spectrum is specified. If the half-width of the tentative peak is 30 cm ^-1 or more, the tangent of the curve curve is convex downward in the range of 600 cm ^-1 centered on the tentative peak and the tangent line is taken as the background Do. If the half-width of the provisional peak is 10 cm ^-1 or less, a tangent line is drawn that is tangent to the local minimum value where the curve of the spectrum is convex downward within a range of three times the half-width about the provisional peak As background. If the background does not have a large slope, the peaks and maxima almost coincide. At a peak of 500 cm ^-1 or less, the background slope becomes large.

(12) The coated member according to the embodiment is
A coated member comprising a substrate and a hard carbon-based film formed on at least a part of the substrate,
The hard carbon-based film includes at least one of a hydrogen atom and an oxygen atom, and a site having a peak of D band and a peak of G band in Raman spectroscopy,
Further, (a) a peak position at 910 ± 50 cm ⁻¹ in Raman spectroscopy (b) a peak position at 810 ± 30 cm ⁻¹ in Raman spectroscopy (c) a peak position in Raman spectroscopy at 705 ± 30 cm ⁻¹ The site of (d) the peak position in Raman spectroscopy is 535 ± 30 cm ⁻¹ (e) the site of peak position in Raman spectroscopy is 260 ± 20 cm ⁻¹ (f) the peak position in Raman spectroscopy is 210 ± 20 cm ^{− 1} site (g) The site where the peak position in Raman spectroscopy is 135 ± 20 cm ⁻¹ (h) the site where the peak position in Raman spectroscopy is 95 ± 10 cm ⁻¹ (i) the peak position in Raman spectroscopy is 2327 ± 10 cm site of ^-1, at least one.

In the above (a) to (i), a portion having a peak value of 1⁄5 or more of the peak height of D band, more preferably a portion having a peak value of 1⁄3 or more (hereinafter referred to as N band area) It is. This N band area is considered to be a carbon nanotube, or an SPx bond such as fullerene, or a portion where an SPx-like bond is formed. The hard carbon-based coating preferably contains at least two of (a) to (d), or at least two of (e) to (i). More preferably, the hard carbon-based coating contains at least two of (a) to (d) and at least two of (e) to (i).

The hard carbon-based film includes a portion having a D band peak and a G band peak in Raman spectroscopy and an N band area. The hard carbon-based coating including the N band area improves the bending strength of the coated member. Such hard carbon-based coatings are suitable as coatings for tools or electrode materials. The area ratio of the N band area to the planar area of the hard carbon-based film is, for example, 0.1% or more and 99% or less. The lower limit value of the N band area area ratio is preferably 1% or more, more preferably 5% or more. The upper limit value of the N band area area ratio is preferably 80% or less, more preferably 60% or less. It becomes preferable as a tool or as an electrode.

(13) The member with a film according to the embodiment is
A coated member comprising a substrate and a hard carbon-based film formed on at least a part of the substrate,
The hard carbon coating is hydrogen atom, and at least one of an oxygen atom, and [A] peak position in the Raman spectroscopy at 1335cm ^-1 or 1349cm ^-1 or less, the half width at the peak position is 30 cm ^-1 More than 95cm ^-1 less part,
[B] peak position in the Raman spectroscopy at 1349cm ^-1 or 1370 cm ^-1 or less, the half width at the peak position is 95cm ^-1 or 350 cm ^-1 or less site, and peak positions in the [C] Raman spectroscopy 1300cm ^-1 above 1335Cm ^-1 or less, including the half-width at the peak position ^{1 cm -1} to 29cm ^-1 or less site, at least one.

In the hard carbon-based film obtained by the method for producing a hard carbon-based film according to the embodiment, portions having different bonding states of carbon atoms may be formed in the shape of marble or particles. When the bonding state of the carbon atom at each site is measured by Raman spectroscopy, if any of the above [A], [B], and [C] is satisfied, the bonding state of the carbon atom at that site is the SP3 bond or Recognized as SP3-like binding. Of course, the hard carbon-based film may be composed of only [A], [B], or [C]. Among these, including at least [A] is more preferable than the combination not including [A]. Because [A] has an intermediate property between [B] and [C], it has good affinity to both [B] and [C].

(14) As one form of the member with a coat of the above (13),
The hard carbon coating is further
(A) A site at a peak position of 910 ± 50 cm ⁻¹ in Raman spectroscopy,
(B) a peak position at 810 ± 30 cm ⁻¹ in Raman spectroscopy,
(C) The site of peak position in Raman spectroscopy is 705 ± 30 cm ⁻¹ ,
(D) a peak position in Raman spectroscopy at 535 ± 30 cm ⁻¹ ,
(E) a site at 260 ± 20 cm ⁻¹ in peak position in Raman spectroscopy,
(F) a site at 210 ± 20 cm ⁻¹ in peak position in Raman spectroscopy,
(G) The site of the peak position in Raman spectroscopy is 135 ± 20 cm ⁻¹ ,
(H) A form including at least one of a site having a peak position of 95 ± 10 cm ⁻¹ in Raman spectroscopy and (i) a site having a peak position of 2327 ± 10 cm ⁻¹ in Raman spectroscopy can be mentioned.

The hard carbon-based coating preferably contains at least two of (a) to (d), or at least two of (e) to (i). More preferably, the hard carbon-based coating contains at least two of (a) to (d) and at least two of (e) to (i). Since the above (a) to (i) have strong tensile properties, the toughness of the hard carbon-based film containing hard [A], [B] and [C] is improved.

(15) As one form of the member with a film concerning an embodiment,
The hard carbon-based film can include a form in which at least one of hydrogen atoms and oxygen atoms in total is 0.1 ppb to 10% in atomic ratio.

In the method of manufacturing a hard carbon-based film according to the embodiment, the hard carbon-based film is formed in a state in which hydrogen atoms and oxygen atoms are contained in at least one of the film forming atmosphere and the discharge electrode. Therefore, the hard carbon-based film of the coated member contains at least one of a predetermined amount of hydrogen atoms and oxygen atoms.

Details of Embodiments of the Present Disclosure
First Embodiment
Hereinafter, embodiments of a method for producing a hard carbon-based coating of the present disclosure and a member with a coating will be described with reference to the drawings. The drawings are schematic for clarity of the description unless otherwise stated. Therefore, the size, the positional relationship and the like of the members are described in an exaggeration or an easy-to-see ratio. The parts denoted by the same reference symbols in the drawings indicate the same parts or members. It should be noted that terms referring to directions in the top, bottom, left, and right, and positional relationships are used as needed in reference to the drawings and for convenience of explanation, but the use of those terms is to facilitate understanding of the invention. The technical scope of the present disclosure is not limited by the meaning of the terms.

«Method for producing hard carbon film»
In the method of manufacturing a hard carbon-based film according to the embodiment, a discharge is repeatedly generated between the carbon electrode and the substrate to form a hard carbon-based film on the surface of the substrate. There are three specific manufacturing methods: (1) using alternating current, (2) using direct current, and (3) using pulse voltage. In any method, at least one of the film formation atmosphere and the discharge electrode is performed under the condition including at least one of a hydrogen atom, an oxygen atom, a water molecule, and a carbon dioxide molecule. If the deposition atmosphere is a gas phase, the pressure can be atmospheric pressure. A bubbling gas in which pure water is bubbled can be used as a film formation atmosphere. The bubbling gas contains water molecules for a vapor pressure determined by the temperature of pure water. Therefore, introduction of hydrogen atoms and oxygen atoms to the hard carbon-based film is facilitated by using a bubbling gas for the film formation atmosphere. The bubbling gas is supplied to the periphery of the discharge electrode 1 where film formation is performed. As the bubbling gas, hydrogen gas is also a candidate, but it is generally suitable to use an inert gas such as argon gas and nitrogen gas as the bubbling gas. In addition, the film forming atmosphere may be underwater.

(1) Manufacturing Method Using AC FIG. 1 is a view for explaining a method of manufacturing a hard carbon-based film using AC. A film forming apparatus 10 shown in FIG. 1 includes a discharge electrode 1, a support electrode 3 for supporting a base 20, a power supply 4, and a bias power supply 5. In this example, the base material 20 is placed on the support electrode 3, the discharge electrode 1 is brought close to the base material 20, and an AC voltage is applied between the discharge electrode 1 and the support electrode 3 by the power supply device 4. Further, in this example, a bias potential is applied by the bias power supply 5 so that the support electrode 3 has a negative potential, and the electrode material of the discharge electrode 1 is attracted to the base 20 side. The bias power supply 5 may not be present. By applying an alternating voltage to the discharge electrode 1 in the film forming apparatus 10, the hard carbon-based film 22 composed of the electrode material of the discharge electrode 1 can be formed on the surface 21 of the substrate 20. The hard carbon-based film 22 can be formed in a wide range by scanning the discharge electrode 1 parallel to the surface 21 of the base 20 while applying an alternating voltage to the discharge electrode 1. The scanning may be performed automatically using a device capable of scanning the surface 21 or may be performed manually.

The AC voltage of the power supply 4 is preferably 3.6 kV or more. This is 20% or more larger than the AC voltage in the conventional method of coating a refractory metal (a metal having a melting point higher than 1500 ° C.). The alternating current voltage in the conventional coating method of the high melting point metal is about 1 kV or more and 3 kV or less. In the case of a high melting point metal coating, when the alternating voltage is less than 1 kV, the current during discharge becomes small, the high melting point metal is difficult to melt, the film formation becomes difficult, and when it is more than 3 kV, the impact during discharge becomes large. This is because the irregularities on the surface of the substrate become large, and a flat and homogeneous film can not be obtained while maintaining the original surface shape. Even if the film forming apparatus 10 of FIG. 1 is operated with the same AC voltage as the conventional coating method, a coating of a carbon material can be formed, but the coating becomes a soft coating having many SP2 bonds. Further, if the AC voltage is slightly larger than 3 kV, SP2 bonding, SP2 like bonding, SP3 bonding, and SP3 like bonding form a film inhomogeneously mixed, so in this example, the AC voltage is set to 3.6 kV or more. The alternating voltage in this example is preferably 7 kV or more, more preferably 8 kV or more, and most preferably 9 kV or more.

In order to give high energy instantaneously to the discharge electrode 1, it is effective to increase the frequency of the alternating voltage. For example, the frequency may be a commercial frequency (50 Hz or 60 Hz) or more and 13.56 MHz or less. The preferable range of the frequency is, for example, 50 Hz to 100 MHz, and further 10 kHz to 15 MHz.

In the case where the bias power supply 5 applies a bias potential at which the support electrode 3 (base material 20) has a negative potential, the absolute value of the bias potential is preferably 100 V or more. This is 20% or more larger than the bias potential in the conventional high melting point metal coating method. The bias potential in the conventional coating method is about 30 V or more and 80 V or less. The upper limit of the bias potential in this example is preferably 500 V. Increasing the bias potential is likely to convert SP3 binding to SP3-like binding.

In order to increase the ratio of SP3 bonding and SP3 like bonding in the hard carbon-based film 22, it is effective to control the AC voltage (AC current) and the bias voltage (bias current) independently. For example, when the AC voltage and the bias voltage are higher than 4.2 kV and 112 V, respectively, the hard carbon-based film 22 in which the SP3-like bond is homogeneous is formed. In addition, it is also effective to change the distance between the base 20 and the discharge electrode 1 in order to increase the ratio. This is because a large amount of energy can be applied to the discharge electrode 1 instantaneously. In order to change the distance, for example, the discharge electrode 1 may be vibrated by a vibration device or the like.

For the discharge electrode 1, a conductive carbon material such as graphite is used. The discharge electrode 1 may contain a binder other than carbon that bonds the carbon material. The content of carbon in the discharge electrode 1 is preferably 90% by mass or more, more preferably 95% by mass or more, and most preferably 99% by mass or more. Furthermore, among the elements other than carbon, it is preferable that the covalent bonding element be 50% by mass or more. Furthermore, it is preferable that the carbon material of the discharge electrode has the features of the hard carbon-based coating of the present disclosure.

The support electrode 3 is not particularly limited. For example, as shown in FIG. 1, the support electrode 3 may be a flat plate-like electrode having a planar area larger than the area when the substrate 20 is viewed in plan from the surface 21 side. Moreover, the support electrode 3 can be comprised with Cu (copper) etc. which are excellent in electroconductivity.

In addition, the temperature of the substrate 20 at the time of film formation is preferably 600 ° C. or less. The temperature of the substrate 20 can also be around normal temperature. For example, the film formation atmosphere around the base material 20 at the time of film formation may be a room temperature / air atmosphere. In that case, the hard carbon-based film 22 can be formed with simpler equipment. In the case of the atmosphere, part of nitrogen contained in the atmosphere may be contained in the hard carbon-based film 22. The deposition atmosphere can also be an atmosphere in which nitrogen is 95% by volume or more. By doing so, the hard carbon-based coating 22 containing more nitrogen can be obtained. In order to include atomic nitrogen instead of molecular nitrogen in the hard carbon-based film 22, the hard carbon-based film 22 is formed in a film forming atmosphere containing a gas (such as NH ₃ ) in which atomic nitrogen is easily separated. Is preferred. When the hard carbon-based film 22 containing nitrogen is used, it is preferable because the application range also extends to a material to be cut which reacts with carbon alone. When nitrogen is contained in the hard carbon coating 22 in an atomic ratio of 5% or more, the effect of suppressing the reaction to the material to be machined becomes apparent and becomes remarkable at 10% or more, and is further remarkable at 30% or more become.

The discharge electrode 1 is consumed along with the film formation of the hard carbon-based film 22. Therefore, it is preferable to monitor the distance from the discharge electrode 1 to the substrate 20 and to adjust the distance to be constant. For example, using an apparatus for automatically adjusting the distance, the distance may be kept at 0.5 mm. In addition, the discharge electrode 1 may be mechanically vibrated by a vibration device or the like to rub the discharge electrode 1 on the surface 21 of the base 20. In that case, the gap between the discharge electrode 1 and the base 20 can be periodically opened by the vibration, and the discharge can be generated when the gap is opened. The interval changes between about 0 mm and 1 mm.

(2) Manufacturing Method Utilizing Direct Current FIG. 2 is a view for explaining a method of manufacturing a hard carbon-based film using direct current. In addition to the discharge electrode 1 and the support electrode 3 of FIG. 1, the film forming apparatus 10 shown in FIG. 2 includes a power supply device 4 that generates direct current and a vibration device 6 that vibrates the discharge electrode 1. In this example, the base material 20 is placed on the support electrode 3, the discharge electrode 1 is brought close to the base material 20, and a direct current voltage is applied to the discharge electrode 1 by the power supply device 4. Vibrate. Also in this example, by scanning the discharge electrode 1 parallel to the surface 21 of the base 20, the hard carbon-based film 22 can be formed in a wide range.

The DC voltage of the power supply device 4 is preferably 3.6 kV or more. If the direct current voltage is slightly larger than 3 kV, SP2 bond, SP2 like bond, SP3 bond, and SP3 like bond form a film which is mixed inhomogeneously, so the DC voltage is set to 3.6 kV or more in this example. The direct current voltage in this example is preferably 7 kV or more, more preferably 8 kV or more, and most preferably 9 kV or more.

The vibrating device 6 holds one end of the discharge electrode 1 (opposite to the base 20), and vibrates the discharge electrode 1 periodically. The vibration changes the distance between the discharge electrode 1 and the substrate 20, and when the distance becomes less than a predetermined value, a discharge occurs. The vibrating device 6 is adjusted so that the pulse width of the discharge is less than 100 milliseconds. For example, the frequency of the discharge electrode 1 by the vibration device 6 may be 1 Hz or more, 10 Hz or more, or 50 Hz or more. By instantaneously applying large energy to the discharge electrode 1, the proportion of SP3 bond and SP3 like bond in the hard carbon-based film 22 can be increased.

Also in this example, a bias potential may be applied such that the support electrode 3 has a negative potential. A bias power supply 5 as shown in FIG. 1 can be used to apply a bias potential. The bias potential may be a self bias potential. The illustration of the bias power supply is omitted in FIG.

(3) Manufacturing Method Using Pulse Voltage As described above, it is preferable to instantaneously give large energy to the discharge electrode 1 in order to increase the proportion of SP3 bond and SP3 like bond in the hard carbon-based film 22. . From that point of view, a pulse voltage may be applied to the discharge electrode 1. FIG. 3 is a view for explaining a method of manufacturing a hard carbon-based film using a pulse voltage. A film forming apparatus 10 shown in FIG. 3 includes a charging circuit 11, a discharging circuit 12, and a discharging control unit 13 in addition to the discharge electrode 1, the support electrode 3 and the power supply 4 in FIG. The charging circuit 11 includes a variable resistor 11 r connected to the positive electrode of the power supply device 4 and a variable capacitor 11 c provided on a connection line connecting the positive electrode line and the negative electrode line downstream of the variable resistor 11 r. The discharge circuit 12 includes a variable capacitor 11 c of the charging circuit 11, and a resistor 12 r and an inductor 12 i connected in series to the variable resistor 11 r downstream of the connection line. The discharge control unit 13 changes the values of the variable resistor 11 r and the variable capacitor 11 c. According to the film forming apparatus 10 of this example, the electric power stored in the variable capacitor 11 c of the charging circuit 11 can be applied to the discharge electrode 1 in a pulse shape by the discharge circuit 12. By applying a pulse voltage to the discharge electrode 1, a pulse discharge is generated between the discharge electrode 1 and the base 20, and the hard carbon-based film 22 is formed on the surface 21 of the base 20. . Also in this example, by scanning the discharge electrode 1 parallel to the surface 21 of the base 20, the hard carbon-based film 22 can be formed in a wide range.

The pulsed discharge preferably satisfies any of the following conditions.
・ The voltage between the discharge electrode 1 and the substrate 20 is more than 125 V and the pulse width is less than 1 millisecond. ・ The voltage between the discharge electrode 1 and the substrate 20 is more than 50 V and the pulse width is less than 10 microseconds.

The hard carbon-based film 22 can be formed on the base 20 by controlling the charge circuit 11 and the discharge circuit 12 by the discharge control unit 13 so as to satisfy the above conditions. The voltage between the discharge electrode 1 and the base 20 can be adjusted by changing the values of the variable resistor 11 r and the variable capacitor 11 c by the discharge control unit 13. Also, the pulse width can be adjusted by changing at least one of the resistor 12r and the inductance 12i. The voltage and pulse width between the discharge electrode 1 and the base 20 can be measured by observing with an oscilloscope using a high voltage probe or the like.

In adjusting the pulse width, the discharge electrode 1 may be vibrated. The vibration device 6 shown in FIG. 2 can be used to vibrate the discharge electrode 1.

By increasing the discharge voltage, it is possible to increase the number of SP3 bond and SP3-like bond sites (site of D band) occupied in the hard carbon-based film 22. For example, when achieving D / G> 10.5 mentioned later, it is mentioned that a discharge voltage shall be 400 V or more. On the other hand, by lowering the discharge voltage, the number of SPx bond and SPx-like bond sites occupied in the hard carbon-based film 22 can be increased. For example, the discharge voltage may be 80V or more and less than 110V. A more preferable discharge voltage is 100V or more and less than 110V.

«Member with film»
According to the method of manufacturing the hard carbon-based film described above, the coated member 2 as shown in FIG. 4 can be manufactured. The coated member 2 includes a substrate 20 and a hard carbon-based film 22 formed on at least a portion (here, the surface 21) of the substrate 20.

Examples of the substrate 20 include cemented carbide, iron-based materials, boronitride-based materials, cubic boron nitride-based materials, cermets, Ni-based materials, and conductive ceramics. These materials are mainly constituent materials of tools.

The hard carbon-based film 22 formed by the method for producing a hard carbon-based film described above can be identified by Raman spectroscopy. There are three major ways of identifying. The hard carbon-based film 22 necessarily contains at least one of a hydrogen atom and an oxygen atom.

(1) First Identification Method X, which is the peak position in Raman spectroscopy of hard carbon-based coating 22, and W, which is the half width at the peak position, satisfy the following [condition I].
[Condition I]
38 cm ^-1 <W <500 cm ^-1
16 × (X-1347.5) +39 <W <16 × (X-1335) +39
X <1370 cm ^-1

As already mentioned, in a spectrum obtained by Raman spectroscopy, SP3 bond forms a peak at less than 1325cm ^-1 or 1335cm ^-1, SP3-like binding to the position of less than 1335cm ^-1 or 1400 cm ^-1 Form a peak. Further, in the spectrum obtained by Raman spectroscopy, SP2 bonds FWHM in a position of less than 1500 cm ^-1 or 1650 cm ^-1 to form a peak of less than 20 cm ^-1, SP2-like coupling 1500 cm ^-1 or 1650 cm ^-1 A peak with a half width of 20 cm ^-1 or more is formed at a position of less than 20 cm. Therefore, if the result of measuring the hard carbon-based film by Raman spectroscopy using a laser with an excitation wavelength of 532 nm satisfies the above range, SP3 bond and SP3-like bond are formed in the hard carbon film It can be judged.

The hard carbon coating 22 not only has high hardness, but also has the property of being hard to chip. When the peak position and the half width decrease, the hardness tends to increase, and when the peak position and the half width increase, the fracture resistance tends to increase.

(2) Second specifying method D / G, which is the ratio of the peak intensity of the D band to the peak intensity of the G band in Raman spectroscopy of the hard carbon-based coating, and W, which is the half width of the D band , Satisfy the following [condition II-A] or [condition II-B] or [condition II-C].
・ [Condition II-A]
W ≦ 115 cm ⁻¹
D / G <9.0
80 / (D / G) ^0.5 <W <180 / (D / G) ^0.5
・ [Condition II-B]
115 cm ^-1 <W <500 cm ^-1
D / G <2.8
・ [Condition II-C]
W <50 cm ^-1 (W <30 cm ^-1 is more preferably <20 cm ^-1 )
D / G> 10.5 (more preferably D / G> 50, still more preferably D / G> 300)

As already mentioned, in the present specification, the peaks are formed below 1325Cm ^-1 or 1400 cm ^-1 peak is formed below D band, 1500 cm ^-1 or 1650 cm ^-1 is G-band. That is, the D band corresponds to SP3 binding and SP3 like binding, and the G band corresponds to SP2 binding and SP2 like binding. Therefore, if the peak intensity ratio D / G of both bands and the half width W in the D band satisfy the above ranges, it can be determined that SP3 bond and SP3 like bond are formed in the hard carbon-based film. .

The hard carbon-based coating 22 not only has high hardness, but also has the property of being hard to chip and hard to wear. As D / G increases, the wear resistance tends to increase, and as the half width increases, the fracture resistance tends to increase.

(3) Third Specific Method In the hard carbon-based film 22 obtained by the method for producing a hard carbon-based film according to the embodiment, it is possible that portions having different bonding states of carbon atoms are formed in a marbled or granular form. is there. In that case, the hard carbon-based film 22 includes at least one of a portion satisfying the following [condition III-A], a portion satisfying [condition III-B], and a portion satisfying [condition III-C].
・ [Condition III-A]
Peak position in the Raman spectroscopy at 1335cm ^-1 or 1349cm ^-1 or less, the half width at the peak position is 30 cm ^-1 or more 95cm ^-1 or less. Half width is preferably further 30 cm ^-1 or more 90cm ^-1 or less, 40 cm ^-1 or more 73cm ^-1 more preferably less, 62cm ^-1 or 73cm ^-1 or less is most preferred.
・ [Condition III-B]
Peak position in the Raman spectroscopy at 1349cm ^-1 or 1370 cm ^-1 or less, the half width at the peak position is 95cm ^-1 or 350 cm ^-1 or less. The peak position is further preferably 1350 cm ^-1 or more and 1365 cm ^-1 or less. Further, the half width is more preferably 120 cm ^-1 or more 350 cm ^-1 or less, 130 cm ^-1 or more 300 cm ^-1 or less is most preferred.
・ [Condition III-C]
Peak position in the Raman spectroscopy at 1300 cm ^-1 or 1335cm ^-1 or less, the half width at the peak position ^{1 cm -1} or more 29cm ^-1 or less.

If the site measured by Raman spectroscopy satisfies any of the above [conditions III-A], [conditions III-B], and [conditions III-C], the bonding state of the carbon atom of that site is the SP3 bond. Or recognized as SP3-like binding. Among these, including at least [condition III-A] is more preferable than the combination not including [condition III-A]. This is because the site of [Condition III-A] has an intermediate property between the site of [Condition III-B] and the site of [Condition III-C], so that the overall affinity is improved.

The hard carbon-based coating 22 may include a portion satisfying [conditions IV-A] to [conditions IV-I] described in the following items.

(4) Fourth Specific Method In hard carbon-based film 22 obtained by the method for producing a hard carbon-based film according to the embodiment, it is possible that portions having different bonding states of carbon atoms are formed in a marbled or granular form. is there. In that case, the hard carbon coating 22 has a portion of the D band formed 1325Cm ^-1 or 1400 cm ^-1 or less, the site of the G band formed in 1500 cm ^-1 or 1650 cm ^-1 or less, further below A site (N band area) satisfying at least one of [Condition IV-A] to [Condition IV-I] is included.
・ [Condition IV-A]
Peak position in Raman spectroscopy is in the range of 910 ± 50 cm ⁻¹ . The preferred range of peak positions is 910 ± 30 cm ⁻¹ , and the more preferred range is 910 ± 10 cm ⁻¹ . The half width of the peak is less than 200 cm ^-1 . The preferred full width at half maximum of the peak is less than 100 cm ⁻¹ , and the more preferred half width is less than 70 cm ⁻¹ .
・ [Condition IV-B]
Peak position in Raman spectroscopy is in the range of 810 ± 30 cm ⁻¹ . The preferred range of peak positions is 810 ± 20 cm ⁻¹ , and the more preferred range is 815 ± 10 cm ⁻¹ . The half width of the peak is less than 200 cm ^-1 , the preferred half width of the peak is less than 100 cm ^-1 , and the more preferred half width is less than 70 cm ^-1 .
・ [Condition IV-C]
The peak position in Raman spectroscopy is in the range of 705 ± 30 cm ⁻¹ . A preferred range of peak positions is 705 ± 20 cm ⁻¹ , and a more preferred range is 705 ± 10 cm ⁻¹ . The half width of the peak is less than 200 cm ^-1 . The preferred full width at half maximum of the peak is less than 100 cm ⁻¹ , and the more preferred half width is less than 70 cm ⁻¹ .
・ [Condition IV-D]
Peak position in Raman spectroscopy is in the range of 535 ± 30 cm ⁻¹ . The preferred range of the peak position is 535 ± 20 cm ⁻¹ , more preferably 535 ± 15 cm ⁻¹ , and still more preferably 505 ± 10 cm ⁻¹ . The half value width of the peak position is less than 800 cm ^-1 . The preferred full width at half maximum of the peak is less than 300 cm ⁻¹ , and the more preferred half width is less than 100 cm ⁻¹ .
・ [Condition IV-E]
The peak position in Raman spectroscopy is in the range of 260 ± 20 cm ⁻¹ . A preferred range of peak positions is 260 ± 15 cm ⁻¹ , and a more preferred range is 260 ± 10 cm ⁻¹ . The half width of the peak is less than 100 cm ^-1 . The preferred full width at half maximum of the peak is less than 80 cm ^-1 , and the more preferred half width is less than 50 cm ^-1 .
・ [Condition IV-F]
Peak position in Raman spectroscopy is in the range of 210 ± 20 cm ⁻¹ . The preferable range of the peak position is 210 ± 15 cm ⁻¹ , and the more preferable range is 210 ± 10 cm ⁻¹ . The half width of the peak is less than 100 cm ^-1 . The preferred full width at half maximum of the peak is less than 80 cm ^-1 , and the more preferred half width is less than 50 cm ^-1 .
・ [Condition IV-G]
Peak position in Raman spectroscopy is in the range of 135 ± 20 cm ⁻¹ . The preferred range of the peak position is 135 ± 15 cm ⁻¹ , and the more preferred range is 135 ± 10 cm ⁻¹ . The half width of the peak is less than 80 cm ^-1 . The preferred full width at half maximum of the peak is less than 40 cm ^-1 , and the more preferred half width is less than 20 cm ^-1 .
・ [Condition IV-H]
Peak position in Raman spectroscopy is in the range of 95 ± 10 cm ⁻¹ . The preferred range of the peak position is 95 ± 8 cm ⁻¹ , and the more preferred range is 95 ± 5 cm ⁻¹ . The half width of the peak is less than 20 cm ^-1 . The preferred full width at half maximum of the peak is less than 10 cm ⁻¹ , and the more preferred half width is less than 5 cm ⁻¹ .
・ [Condition IV-I]
The peak position in Raman spectroscopy is in the range of 2327 ± 10 cm ⁻¹ . The preferable range of the peak position is 2327 ± 7 cm ⁻¹ , and the more preferable range is 2327 ± 5 cm ⁻¹ . The half width of the peak is less than 16 cm ^-1 . The preferred full width at half maximum of the peak is less than 8 cm ⁻¹ , and the more preferred half width is less than 5 cm ⁻¹ .

The N band area is recognized in fibrous carbon materials and in conductive conductive carbon materials having lubricity. The fibrous carbon material is considered to be effective in increasing the bending strength of the tool on which the hard carbon-based coating 22 is formed. On the other hand, it is considered that the conductive carbon material having lubricity is effective in reducing the cutting resistance of the tool on which the hard carbon-based film 22 is formed. Therefore, it is expected that the tool provided with the hard carbon-based film 22 including the N band area will be a tool having excellent bending strength, fracture resistance and wear resistance.

Further, it is considered that the conductive and conductive carbon material has an effect of increasing the durability of the electrode material on which the hard carbon-based film 22 is formed and the capacity of the battery. Therefore, it is expected that the electrode material provided with the hard carbon-based film 22 including the N band area has excellent durability and can produce a high capacity battery.

Here, in the N band area, the peak of the D band is also detected. N / D can be used to identify the N band area with a Raman image. N / D is the ratio of the peak intensity of the N band to the peak intensity of the D band. The preferable range of N / D is 1/5 or more and 15 or less. More preferable N / D is 1/3 or more and 6 or less.

The hard carbon-based film 22 contains at least one of hydrogen atoms and oxygen atoms in total in an amount of 0.1 ppb or more and 10% or less in atomic ratio. This is because the film forming atmosphere and the discharge electrode 1 contain hydrogen atoms and oxygen atoms.

The hard carbon-based film 22 may contain atoms other than carbon. For example, a form containing nitrogen of 5 atomic% or more and 60 atomic% or less or a form containing boron of 5 atomic% or more and 50 atomic% or less can be mentioned. In the former form, carbon nitride is contained in the hard carbon-based film 22, and in the latter form, boronitride carbon is contained in the hard carbon-based film 22. In addition, the hard carbon-based film 22 may contain aluminum, silicon and phosphorus in a total amount of 5 atomic% or more and 50 atomic% or less.

(Other configuration)
The surface roughness Ra of the hard carbon-based film 22 is preferably 0.1 μm or more. If the surface roughness Ra of the hard carbon-based film 22 is 0.1 μm or more, the adhesion becomes strong. Here, Ra in the present specification is an arithmetic mean roughness defined in JIS B 0601 (2001).

The thickness of the hard carbon-based film 22 can be selected as appropriate. For example, the thickness of the hard carbon-based film 22 may be 10 μm or less. The thickness is not necessarily uniform, and the thickness of the thickest portion may be 10 μm or less. By setting the thickness to 10 μm or less, peeling of the hard carbon-based coating 22 can be easily suppressed. The thickness can be adjusted by changing the scanning speed of the discharge electrode 1 of FIGS. It is also possible to further scan the top of the hard carbon-based coating 22 with the discharge electrode 1 to make the hard carbon-based coating 22 thicker.

The average particle diameter of the hard carbon-based film 22 is preferably 10 μm or less. If the average particle diameter of the hard carbon-based film 22 is 10 μm or less, the toughness of the hard carbon-based film 22 can be improved. The average particle size of the hard carbon-based coating 22 can be determined by microscopic observation of the hard carbon-based coating 22. Specifically, the area of 10 or more crystal particles is measured, and the diameter of a circle equivalent to the area of each particle is determined. The average value of the determined diameters is the average particle diameter of the hard carbon-based coating 22.

Moreover, it is preferable that surface roughness Ra of the surface 21 of the base material 20 in which the hard carbon-type film 22 is formed is also 0.1 micrometer or more. If the surface roughness Ra of the substrate 20 is 0.1 μm or more, the bonding area between the substrate 20 and the hard carbon-based film 22 becomes large, and the hard carbon-based film 22 becomes difficult to peel off.

Between the surface 21 of the base material 20 and the hard carbon-based film 22, an intermediate layer 23 may be provided to improve the adhesion between the two. The intermediate layer 23 may be a metal layer or a composite metal layer containing at least one of Ni, Ti, Zr, Hf, Nb, Ta, Mo, and W. Further, as the intermediate layer 23, ceramic layers or laminated ceramics containing at least one of TiN, ZrN, HfN, NbN, TaN, NbC, TaC, MoC and WC may be mentioned. The average thickness of the intermediate layer 23 is preferably 10 μm or less.

<Test example>
The film-coated member 2 provided with the hard carbon-based film 22 shown in FIG. 4 was produced using the film forming apparatus 10 of any of FIGS.
«Test 1»
In the test 1, the hard carbon-based film 22 was formed by the film forming apparatus 10 (without the bias power supply 5) using the direct current shown in FIG. First, the base material 20 of 30 mm × 30 mm × 1 mm t of Mo or tungsten carbide (WC) was placed on the support electrode 3 made of Cu of 100 mm × 100 mm × 5 mm t size. Next, while applying a direct current voltage of 3.8 kV or 4.0 V, 60 Hz between the support electrode 3 and the discharge electrode 1 made of a carbon rod, the discharge electrode 1 was brought close to the substrate 20 so as not to be in contact. An alternating current flowed about 0.4 A between the discharge electrode 1 and the substrate 20 at the time of discharge. Since the vibration of 60 Hz was applied to the discharge electrode 1, a discharge occurred when the separation distance between the discharge electrode 1 and the base material 20 became close during the vibration. The film forming atmosphere was a mixed atmosphere of argon (Ar) and pure water (H ₂ O). Specifically, Ar gas was bubbled into pure water maintained at 60 ° C. in a container, and the hard carbon-based film 22 was formed on the substrate 20 in the pure water.

Since the hard carbon-based film 22 was formed on the substrate 20, it was evaluated by Raman spectroscopy using a laser with an excitation wavelength of 532 nm. In the evaluation, a 100 μm square area including the two-dimensional center of gravity of the coated area of the hard carbon coating 22 is analyzed by the mapping function or imaging function of the Raman spectrometer, and the Raman image displayed by color coding or gray level depending on the characteristics. Was produced. Among the Raman images, the main portion in which the D band occupies more than 50% in area ratio was identified, and the Raman peak and the half width of the main portion were examined. The results are shown in Table 1. The Raman peak (1) in Table 1 is the peak detected in the main portion and is the largest peak among the D bands indicating the presence of SP3 binding and SP3 like binding. The Raman peak (2) is the peak detected in the main portion and is the largest peak among the G bands indicating the presence of SP2 binding and SP2-like binding. Also, D / G is a peak ratio obtained by dividing the peak intensity of the D band by the peak intensity of the G band. The meanings of the terms in these tables are the same as in Tables 2 to 6 described later.

Moreover, the area ratio (area ratio) of the said main part to the planar area of the hard carbon-type film 22 of each sample was investigated. The area ratio was obtained by calculation using a color-coded Raman image or a Raman image displayed in gray scale. Furthermore, the amount of hydrogen atoms (H), oxygen atoms (O), and argon atoms (Ar) contained in the hard carbon-based film 22 of each sample was determined. The element content (atomic%) was determined by a general procedure using secondary ion mass spectrometry. These results are also shown in Table 1.

As shown in Table 1, Sample 1-1, and SP3-like coupling half width 52cm ^-1 at the peak position 1346Cm ^-1, the spectrum of the SP2-like coupling half width 55cm ^-1 is confirmed by the peak position 1581 cm ^-1 The Further, in the sample 1-2, and SP3-like coupling half width 55cm ^-1 at the peak position 1348Cm ^-1, the spectrum of the SP2-like coupling half width 50 cm ^-1 was confirmed by the peak position 1585 cm ^-1. The coatings of these samples 1-1 and 1-2 are hard carbon-based coatings 22 which simultaneously satisfy [conditions I], [conditions II-A] and [conditions III-A] described in the item of coated member 2 It turned out that there is.

In addition, the area ratio of Sample 1-1 was 81%, and the area ratio of Sample 1-2 was 85%. That is, it has been found that the ratio of the main portion to the planar area of the hard carbon-based coating 22 is very high.

Furthermore, it was found that in each sample, hydrogen atoms and oxygen atoms in total were contained at 0.1 ppm or more and 5% or less in atomic ratio. It was also found that each sample contained an argon atom. These atoms are considered to be derived from the film forming atmosphere.

«Test 2»
In Test 2, samples 5-1 to 5-11 were produced in which the hard carbon-based coating 22 was formed on the base 20 using the film forming apparatus 10 using the pulse discharge of FIG. The substrate 20 was any of a cemented carbide, a cemented carbide having an intermediate layer 23, Ta, Mo, Nb, high-speed steel, or Al. The intermediate layer 23 was a Ni plating layer or a TiN plating layer. The film forming apparatus 10 was adjusted so that the conditions for pulse discharge satisfied either of the following [A] and [B]. The surface 21 was scanned with the discharge electrode 1 so that the discharge electrode 1 was rubbed on the surface 21 of the substrate 20 while being vibrated at 30 Hz, 60 Hz, or 90 Hz.
[A] The voltage between the discharge electrode 1 and the substrate 20 is more than 50 V and the pulse width is less than 10 microseconds [B] The voltage between the discharge electrode and the substrate is more than 125 V and the pulse width is 1 millisecond Less than

The film formation atmosphere of each sample is as follows.
・ Samples 2-1 to 2-3
Deposition atmosphere: hydrogen (H ₂ ) gas (100%)
・ Samples 2-4 to 2-6
Deposition atmosphere: carbon dioxide (CO ₂ ) gas (100%)
・ Samples 2-7 and 2-8
Film forming atmosphere: Ar gas (100%) bubbling pure water at 60 ° C.
Samples 2-9 to 2-11
Film forming atmosphere: N ₂ gas (100%) bubbling pure water at 60 ° C.
Here, only the discharge electrode 1 used for the preparation of the samples 2-7 and 2-8 was used which contained 5 atomic% of hydrogen.

When each sample was examined by Raman spectroscopy, areas with different characteristics were formed in a marble shape. The results of examining the peaks in each area are shown in Tables 2 and 3. Each sample contained a first area, a second area and a fourth area, and some samples also included a third area. The first area is an area including a portion in which the D band and the G band are mixed. The second area is an area including a portion satisfying [condition III-A] or [condition III-B]. The third area is an area including a portion satisfying [Condition III-C]. The fourth area is an area (same as N band area) including a portion satisfying any of [condition IV-A] to [condition IV-I].

The graph which plotted the result of Table 2 (result of 1st area) is shown to FIG. The horizontal axis of the graph in FIG. 5 represents the peak position (cm ^-1 ) of the Raman peak (1), and the vertical axis represents the half width (cm ^-1 ) of the Raman peak (1). It is the range which satisfy | fills condition I]. On the other hand, the horizontal axis of the graph in FIG. 6 is D / G, and the vertical axis is the half width (cm ⁻¹ ) of the Raman peak (1). A portion surrounded by two curves in FIG. 6, a broken line in the horizontal direction indicating the position of 115 cm ⁻¹ in half width, and a broken line in the vertical direction indicating the position of 9.0 in D / G It is the range which satisfies-A]. Further, a portion surrounded by a broken line in the horizontal direction indicating the position of 115 cm ^-1 in the half width in FIG. 6 and a dotted line in the vertical direction indicating the position of D / G of 2.8 corresponds to [Condition II-B]. It is a range that meets.

As shown in FIG. 6, most of the samples satisfy [condition II-A] or [condition II-B], but some of the samples satisfy [condition II-A] or [condition II-B]. I do not meet. However, as shown in FIG. 5, it was found that all the samples satisfied [condition I], and the coatings of all the samples were hard carbon-based coatings 22.

From the results in Table 2, samples 2-4, 2-5, 2-6 having a discharge voltage of 110 V tended to have higher Raman peaks (1) than the other samples having a discharge voltage of more than 125 V. . Samples 2-4, 2-5, and 2-6 satisfy [Condition III-B], and the other samples satisfy [Condition III-A].

Further, from the results of Tables 2 and 3, it was found that in the hard carbon-based film 22 of Test 2, the first area occupies about 50% or more, and the second area occupies about 20 to about 30%. The hard carbon-based film 22 of each sample contained a predetermined amount of hydrogen atoms or oxygen atoms.

«Test 3»
In test 3, samples 3-1 to 3-3 are manufactured using the same materials and methods as samples 2-9 to 2-11 in test 2 except that the bubbling gas in the film formation atmosphere of the liquid phase is different from that of discharge electrode 1 did. The discharge electrode 1 contains 98% by mass of carbon and 2% by mass of nitrogen, and was manufactured by a vapor phase synthesis method. The bubbling gas was nitrogen (100%).

The nitrogen content contained in the hard carbon-based coating 22 of Samples 3-1 to 3-3 was measured. The results are shown in Table 4. The content of nitrogen in the hard carbon-based coating 22 was determined by a general procedure using energy dispersive X-ray analysis. The nitrogen content is an average value in a 100 μm square including the center of the sample (the two-dimensional center of gravity of the coating area). It was confirmed by Raman spectroscopy that the hard carbon-based film 22 of all the samples satisfied [Condition I] and [Condition II-A].

As shown in Table 4, from the results of Samples 3-1, 3-2, and 3-3, it was found that the amount of nitrogen contained in the hard carbon-based film 22 increases as the pulse voltage width increases.

«Test 4»
In Test 4, samples 4-1 to 4-3 in which the hard carbon-based coating 22 was formed on the base material 20 were produced using the film forming apparatus 10 using the pulse discharge of FIG. The base 20 was Ta. The discharge voltage was 500 V or 800 V, the pulse voltage width was 0.7 or 0.9, and the vibration frequency of the discharge electrode 1 was 180 Hz or 360 Hz. In addition, the film formation atmosphere was the same as Samples 2-7 to 2-8 in Test 2. The film formation conditions of each sample and the measurement results of Raman spectroscopy are shown in Table 5. As shown in Table 5, hydrogen atoms and oxygen atoms were also confirmed in the hard carbon-based film 22 in Samples 4-1 to 4-3.

As shown in Table 5, all of the samples 4-1 to 4-3 satisfied the [condition II-C]. Condition II-C specifies that the half width of D band (Raman peak (1)) is less than 50 cm ^-1 and D / G is more than 10.5 (the alternate long and short dash line shown in the graph of FIG. See the section enclosed by). The D / G values of Samples 4-1 to 4-3 are all extremely large. That is, in the samples 4-1 to 4-3, the D band is extremely dominant. Since the D band is a band corresponding to the SP3 bond and the SP3 like bond, the hard carbon-based film 22 of the samples 4-1 to 4-3 is a film in which the ratio of the SP3 bond and the SP3 like bond is extremely high.

In Test 4, the discharge voltage is set higher than in Test 2. It is inferred that this contributes to increasing the D / G of the hard carbon-based coating 22. In particular, when samples 4-1 and 4-2 are compared, it can be seen that D / G increases significantly as the discharge voltage increases. In addition, it was found that D / G can be increased by increasing the vibration frequency of the discharge electrode 1 by comparing the sample 4-1 with the sample 4-3.

«Test 5»
In Test 5, samples 5-1 to 5-12 having the hard carbon-based film 22 were produced in the same manner as in Test 2. The substrate 20 was Ta, Cu or Al. The discharge voltage was 100 V, 102 V, 105 V or 108 V, the pulse voltage width was 0.005 msec, 0.007 msec, 0008 msec or 0.009 msec, and the vibration frequency of the discharge electrode 1 was 90 Hz or 120 Hz. The film formation conditions of each sample and the measurement results of Raman spectroscopy are shown in Table 6. In the hard carbon-based film 22 of each sample, the fourth area (a portion satisfying [Condition IV-A] to [Condition IV-I]) occupies the largest area. Therefore, Table 9 shows only the measurement results of the fourth area. Table 6 also shows the ratio (N / D) of the peak intensity of the N band to the peak intensity of the D band.

As shown in Table 6, among the samples 5-1 to 5-12 [conditions IV-A] to [conditions IV-I], the fourth area in which the portions satisfying the two conditions are mixed occupies the majority. The peak of this is a peak close to a carbon nanotube or a Raman peak such as fullerene. In Test 5, the discharge voltage is set to about 100 V to 110 V, and the vibration frequency of the discharge electrode 1 is set to about 90 Hz to 120 Hz. That is, in the test 5, the discharge voltage is set lower than in the test 2. It is presumed that this contributes to enlarging the fourth area occupied in the hard carbon-based coating 22.

It should be understood that the embodiments disclosed herein are illustrative in all respects and not restrictive. The scope of the present invention is shown not by the embodiments described above but by the scope of claims, and is intended to include meanings equivalent to the scope of claims and all modifications within the scope.

DESCRIPTION OF SYMBOLS 10 film-forming apparatus 11 charge circuit 11r variable resistance 11c variable capacitor 12 discharge circuit 12r resistance 12i inductor 13 discharge control part 1 discharge electrode 2 member with film 20 base material 21 surface 22 hard carbon system film 23 middle layer 3 support electrode 4 power supply device 5 Bias power supply 6 Vibration device

Claims (15)

A film forming apparatus having a power supply device and a discharge electrode containing a carbon material, and a step A of preparing a substrate having a surface on which a film is to be formed,
A step B of forming a hard carbon-based film on the surface by repeatedly generating a discharge between the discharge electrode and the base material under a predetermined film forming atmosphere by the film forming apparatus;
The process B is
The method for producing a hard carbon-based film, which is performed under the condition that at least one of the film forming atmosphere and the discharge electrode contains at least one of a hydrogen atom, an oxygen atom, a water molecule, and a carbon dioxide molecule. The method for producing a hard carbon-based film according to claim 1, wherein the deposition atmosphere is atmospheric pressure. The method for producing a hard carbon-based film according to claim 1, wherein the deposition atmosphere is water. The power supply device is an alternating current power supply,
The method for producing a hard carbon-based film according to any one of claims 1 to 3, wherein an alternating voltage applied to the discharge electrode is 3.6 kV or more. The power supply device is a DC power supply,
The DC voltage applied to the discharge electrode is 3.6 kV or more,
The method for producing a hard carbon-based film according to any one of claims 1 to 3, wherein the discharge electrode is periodically vibrated to generate a discharge having a pulse width of less than 100 milliseconds. The film forming apparatus is
A charging circuit for storing power from the power supply device;
A discharge circuit for discharging the power of the charging circuit in a pulse shape;
A discharge between the discharge electrode and the substrate with a voltage greater than 125 V and a pulse width less than 1 millisecond, or a voltage between the discharge electrode and the substrate with a voltage greater than 50 V and a pulse width less than 10 microseconds The method for manufacturing a hard carbon-based film according to any one of claims 1 to 3, further comprising: a discharge control unit that controls the discharge circuit so as to generate the discharge. The substrate according to any one of claims 1 to 6, wherein the substrate is made of cemented carbide, iron-based material, boronitride-based carbon material, cubic boron nitride-based material, cermet, Ni-based material, or conductive ceramic. The manufacturing method of the hard carbon-type film of 1 item. The method for manufacturing a hard carbon-based film according to any one of claims 1 to 7, wherein the discharge electrode is a carbon material containing 90 mass% or more of carbon atoms. The method for producing a hard carbon-based film according to any one of claims 1 to 7, wherein the discharge electrode contains a carbon atom, a boron atom, and a nitrogen atom in a total amount of 90% by mass or more. A coated member comprising a substrate and a hard carbon-based film formed on at least a part of the substrate,
The hard carbon-based film contains at least one of a hydrogen atom and an oxygen atom,
A coated member, wherein X being a peak position in Raman spectroscopy of the hard carbon-based coating and W being a half width at the peak position satisfy the following conditions.
38 cm ^-1 <W <500 cm ^-1
16 × (X-1347.5) +39 <W <16 × (X-1335) +39
X <1370 cm ^-1 A coated member comprising a substrate and a hard carbon-based film formed on at least a part of the substrate,
The hard carbon-based film contains at least one of a hydrogen atom and an oxygen atom,
D / G which is a ratio of the peak intensity of D band to the peak intensity of G band in Raman spectroscopy of the hard carbon-based film, and W which is the half width of the D band,
W ≦ 115 cm ⁻¹ , and D / G <9.0 and 80 / (D / G) ^0.5 <W <180 / (D / G) ^0.5 or 115 cm ⁻¹ <W <500 cm ⁻¹ And a coated member that satisfies D / G <2.8 or W <50 cm ⁻¹ and 10.5 <D / G. A coated member comprising a substrate and a hard carbon-based film formed on at least a part of the substrate,
The hard carbon-based film includes at least one of a hydrogen atom and an oxygen atom, and a site having a peak of D band and a peak of G band in Raman spectroscopy,
Furthermore, the peak position in Raman spectroscopy is a site at 910 ± 50 cm ⁻¹ ,
The peak position in Raman spectroscopy is a site at 810 ± 30 cm ⁻¹ ,
The site where the peak position is 705 ± 30 cm ⁻¹ in Raman spectroscopy,
The peak position in Raman spectroscopy is a site at 535 ± 30 cm ⁻¹ ,
The peak position in Raman spectroscopy is a site of 260 ± 20 cm ⁻¹ ,
The site of peak position at 210 ± 20 cm ⁻¹ in Raman spectroscopy,
The site of the peak position 135 ± 20 cm ⁻¹ in Raman spectroscopy,
A coated member comprising at least one of a site with a peak position of 95 ± 10 cm ⁻¹ in Raman spectroscopy and a site with a peak position of 2327 ± 10 cm ⁻¹ in Raman spectroscopy. A coated member comprising a substrate and a hard carbon-based film formed on at least a part of the substrate,
The hard carbon coating is hydrogen atom, and at least one of an oxygen atom, and the peak position in the Raman spectroscopy at 1335cm ^-1 or 1349cm ^-1 or less, the half width at the peak position is 30 cm ^-1 or more 95cm ^{- 1} part or less,
Peak position in the Raman spectroscopy at 1349cm ^-1 or 1370 cm ^-1 or less, a half value width 95cm ^-1 or 350 cm ^-1 or less site at the peak position, and the peak position is 1300 cm ^-1 or more in the Raman spectroscopy 1335Cm ^-1 hereinafter, the half value width of ^{1 cm -1} or more 29cm ^-1 or less site at the peak position, a coated member comprising at least one. The hard carbon-based coating further has a peak position of 910 ± 50 cm ⁻¹ in Raman spectroscopy,
The peak position in Raman spectroscopy is a site at 810 ± 30 cm ⁻¹ ,
The site where the peak position is 705 ± 30 cm ⁻¹ in Raman spectroscopy,
The peak position in Raman spectroscopy is a site at 535 ± 30 cm ⁻¹ ,
The peak position in Raman spectroscopy is a site of 260 ± 20 cm ⁻¹ ,
The site of peak position at 210 ± 20 cm ⁻¹ in Raman spectroscopy,
The site of the peak position 135 ± 20 cm ⁻¹ in Raman spectroscopy,
The peak position in Raman spectroscopy includes at least one of a site of 95 ± 10 cm ^{−1 and} a peak position in Raman spectroscopy of 2327 ± 10 cm ^−1. The coated member as described. The member with a film according to any one of claims 9 to 13, wherein the hard carbon-based film contains at least one of hydrogen atoms and oxygen atoms in total in an atomic ratio of 0.1 ppb to 10%.

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