JP5898437B2 - Amorphous carbon film laminated member and manufacturing method thereof - Google Patents

Description

  The present invention relates to an amorphous carbon film laminated member and a method for manufacturing the same, and in particular, the amorphous carbon film is used as a countermeasure for static elimination such as a feeder for conveying parts and materials, a carrier, a tray for handling, or the like. The present invention relates to an amorphous carbon film laminated member used for an electrode, a separator, and the like, and a manufacturing method thereof.

  An amorphous carbon film or an amorphous carbon film containing silicon or the like (hereinafter collectively referred to as an “amorphous carbon film”) is hard and excellent in wear resistance, has a small friction coefficient, and has a high cohesiveness against a soft metal. It also has anti-sticking properties, can give high functionality to the surface of the base material, and has begun to be used in a wide range of industrial fields, mainly for feeders and carriers for small parts and materials, and trays for handling. Yes.

The amorphous carbon film depends on the film forming conditions such as the film thickness, the source gas and the post-treatment, but the volume resistivity related to the conductivity is about 10 ⁸ to 10 ¹² Ω · cm, It has a personality. For this reason, the amorphous carbon film is made of powder such as mabushi powder which is added to facilitate and smooth the transportation of the aforementioned parts and materials, etc. ) (Referred to as “parts”) as a coating material for transport feeders, carriers, handling trays, etc., as a general method for preventing electrostatic adhesion of such parts, the amorphous carbon film thickness is sufficiently thin. Further, by connecting the conductive base material on which the amorphous carbon film is formed to a reference potential point (ground, etc.) with an electric conductor, that is, grounding, the workpiece is connected to the amorphous carbon film. Static electricity generated by contact is removed to the ground through the amorphous carbon film and further through the base material, so that the work can be prevented from adhering to the amorphous carbon film coated on the base material.
However, as the size of the parts that come into contact with and slide on the amorphous carbon film is miniaturized, the static removal ability (conductivity) and removal method of the conventional amorphous carbon film are insufficient, and the amorphous due to static electricity. Phenomena such as adhesion and residue on the surface of carbonaceous carbon films have been confirmed.
Today, the number of portable electronic devices is increasing, and the parts used are also becoming smaller. In such a situation, residue due to sticking of parts in the process of parts transportation, alignment for parts processing, storage, etc. in the production process of micro parts can lead to different performance lots of parts with different performances. And problems such as loss of traceability due to mixing between production lots, causing serious problems in quality control of production processes.

In a lithium ion battery, an amorphous carbon film is formed on the surface of a metal electrode foil (metal current collector) used as a positive electrode plate in order to improve the corrosion resistance and conductivity (Patent Document 1). . Also in the fuel cell separator, the entire surface of the low electrical resistance metal plate is covered with an amorphous carbon film having good electrical conductivity and corrosion resistance (Patent Document 2). However, when the amorphous carbon film is formed thick, there is a possibility that the conductivity is rather lowered. In addition, the electrolyte solution may penetrate through the film defects such as pinfall caused by abnormal discharge etc. in the film formation process of the amorphous carbon film, and the electrode metal may be corroded and the electrode metal may be corroded. There is also.
In addition, even when an ordinary amorphous carbon film is formed very thin, it can be energized through the amorphous carbon film due to a tunnel effect or the like. Continuity etc. will be significantly impaired.

On the other hand, a volume electrical resistance of about 10 ⁶ Ω · cm is applied to a material of aluminum or an aluminum alloy, which is called “conductive anodized”, as another anti-abrasion / soft metal adhesion prevention and low friction surface treatment. In some cases, the amount of charge of the workpiece in contact with the film is suppressed by anodizing so as to maintain the rate and forming the film on the substrate thinner (see Patent Document 3). The electrical resistance value is large, and furthermore, functions such as excellent wear resistance, low friction, and soft metal adhesion prevention like an amorphous carbon film cannot be expressed.

JP 2009-134988 A JP 2000-67881 A JP 2006-291259 A

  In recent years, the amorphous carbon film itself has also been used as a base adhesion layer having a higher electric resistance than a normal amorphous carbon film such as an amorphous carbon film containing silicon, or an amorphous carbon film. In order to improve the durability, there is the present situation that the film is made thicker, and it is difficult to remove static electricity and secure energization by the method that seems to have contributed to the conventional static electricity removal. .

Chip-shaped electronic components used in small electronic devices are called chip resistors, chip LEDs, chip capacitors, and the like, and the size of the components has been reduced, resulting in a 0603 shape (length 0.6 mm × width 0.3 mm × thickness 0. 3 mm) and 0402 shape (vertical width 0.4 mm × lateral width 0.2 mm × thickness 0.2 mm). The small and lightweight chip parts have a weight of about 0.4 to 0.1 mg, and handling such as transportation, alignment or storage in the manufacturing process of these lightweight objects is required. In comparison, even weaker static electricity (electrical attraction) tends to adhere to handling substrates such as feeders for small and lightweight parts, and handling substrates with smaller electrical resistance are required. I came.
Therefore, when using the amorphous carbon film as a coating material such as the above-mentioned transport feeder, carrier, handling tray, etc., a device for removing static electricity from the coated substrate including the amorphous carbon film is more effective. More needed.
Furthermore, the removal of static electricity from handling substrates such as electronic components that may be damaged by static electricity is becoming increasingly important.

  In addition, when a thin amorphous carbon film that exhibits a tunnel effect is formed on the surface of an electrode formed of a conductive material such as various battery electrodes, it is caused by abnormal discharge during the film forming process. Through an amorphous carbon film defect such as a discontinuous state of the amorphous carbon film caused by pin fall and surface irregularities of the electrode substrate, the electrolyte solution penetrates, reaches the base, and the electrode metal corrodes. There is also a problem.

  In view of the current situation, the present invention can be manufactured with a simple configuration and at a low cost. In the transportation / alignment / storage of various parts such as microelectronic parts, and further, various conductivity is achieved with an amorphous carbon film. An object of the present invention is to provide an amorphous carbon film laminated member capable of ensuring electrical conduction through an amorphous carbon film and a substrate when an electrode or the like is coated, and a method for manufacturing the same.

  As a result of intensive studies to achieve the above object, the present inventors have established the following means. That is, after an amorphous carbon film is formed on a substrate, metal plating is partially deposited on the surface layer portion of the amorphous carbon film at intervals of “jumping”, whereby the amorphous carbon film This ensures electrical conductivity with the base material. By this method, in the surface treatment application of the friction / sliding parts described above, the conductive metal plating is present on the surface of the amorphous carbon film in a “flying portion” state. At least a part of the workpiece, such as a component that is supplied on the substrate on which the carbon film is formed and is electrostatically charged due to friction with the substrate, etc., including the presence of the workpiece, the path of movement, etc. It has been found that it is possible to provide a surface laminated member that makes it possible to instantaneously take a physical contact (contact) (to make a contact terminal) and to remove static electricity through the contact. Moreover, when applied to coating materials such as the above-described battery electrodes and separators, it is possible to ensure energization with a lower electrical resistance through the metal plating portion.

The present invention has been completed based on these findings, and according to the present invention, the following inventions are provided.
<1> An amorphous carbon film formed on a substrate, wherein the metal plating is partially deposited on a surface layer portion and / or a defect inner wall portion of the amorphous carbon film. Carbon film laminated member.
<2> The amorphous carbon film laminated member according to <1>, wherein the amorphous carbon film contains silicon.
<3> The amorphous carbon film according to <1> or <2>, wherein the amorphous carbon film is a component transporting member, a component aligning member, or a component storage member having the amorphous carbon film as an uppermost layer. Laminated member.
<4> The amorphous carbon film laminated member according to <1> or <2> above, which is an electrode current collector for a battery.
<5> The amorphous carbon film laminated member according to the above <1> or <2>, which is a separator for a fuel cell.
<6> After an amorphous carbon film is formed on the substrate, metal plating is partially deposited on the surface layer part and / or the defect inner wall part of the amorphous carbon film to thereby form the amorphous carbon film and the substrate. A method for producing an amorphous carbon film laminated member, wherein electrical conductivity with a material is ensured.

According to the present invention, the amorphous carbon film retains the static neutralization effect, and promotes the removal of static electricity generated by transportation, alignment, storage, etc. performed by a method in which a part or the like is brought into contact with the amorphous carbon film. Electrostatic adhesion to the amorphous carbon film such as parts can be suppressed.
In addition, when the present invention is applied to the surface of a conductive substrate such as a battery electrode or separator, it is possible to suppress a decrease in conductivity due to the formation of an amorphous carbon film.

Observation photograph by CCD camera of Example 1 (× 500) Observation photograph by the CCD camera of Example 1 (× 5000) Observation photograph with CCD camera of comparative example (× 500) Observation photograph by CCD camera of Example 2 Photograph showing FIB processed part of Example 2 Cross section observation photograph by FIB-SEM of convex part 1

  In one embodiment of the present invention, after depositing an amorphous carbon film on a substrate, by partially depositing metal plating on a defective portion such as pin fall of the amorphous carbon film, It is characterized by improving and ensuring the electrical conductivity between the amorphous carbon film and the substrate.

First, a substrate, an amorphous carbon film, and a method for forming the amorphous carbon film in the present invention will be described in order.
[Substrate]
In the present invention, the substrate has conductivity such as metals such as iron, copper, aluminum, and titanium, various alloy metal materials such as aluminum alloys and stainless steel (SUS), conductive carbon fibers, and components thereof. In addition, materials such as inorganic materials such as glass, silicon carbide, and ceramics coated with conductive adhesives and resins, conductive metal thin films and metal oxide thin films (ITO, etc.), polyerylene, polypropylene, polystyrene, etc. Various materials can be used depending on the application, such as a polymer material, a plating film having conductivity, or various base materials on which conductive ion plating such as vapor deposition is formed.
As an example of a specific substrate, a ball feeder or linear feeder that moves parts by applying fine vibrations to the parts to be transported through the base material, a room formed to store the parts (cavities) Index carrier that moves parts by storing them in the tee) and discharging them, and when processing and inspecting parts such as hoppers and chutes that move parts while sliding them by gravity, etc. To hold and fix parts at a fixed position, hold parts, etc., and hold and transfer parts holding pallets that form a chamber for positioning (vacuum), etc. At least necessary for feeding feeders for various parts such as jigs such as suction nozzles and suction plates for inspection, and jigs for carriers, parts alignment and storage It is such a part of the surface such.

[Amorphous carbon film]
The amorphous carbon film layer according to an embodiment of the present invention is provided directly on the substrate or indirectly through another layer such as an adhesive layer.
In this specification, an amorphous carbon film is formed with or without hydrogen, and the structure of the film includes both a diamond structure (sp3 bond) and a graphite structure (sp2 bond). It may be amorphous, and the mixing ratio, presence or absence of hydrogen, and content are not particularly limited. Both mixing ratio and hydrogen content can be adjusted arbitrarily.
The amorphous carbon film of this embodiment is formed by various PVD methods and CVD methods.
For example, in the case of the PVD method, various plasma sputtering methods such as dipolar sputtering method, tripolar sputtering method, quadrupole sputtering method, magnetron sputtering method, and counter target sputtering method, ion beam sputtering method, ECR sputtering method, etc. Various ion beam sputtering methods, direct current application (DC) ion plating methods, activated reaction vapor deposition methods (ARE methods), holocathode discharge methods (HCD methods), various methods using plasma such as radio frequency excitation methods (RF methods) Ion plating method, ion cluster beam deposition method (ICB method), ion beam epitaxy method (IBE method), ion beam deposition method (IBD method), ion beam assisted deposition method (IBAD method), ion deposition thin film formation method ( IVD method) Various ion plating methods using a beam, etc. If it is a CVD method, a direct current (DC) plasma CVD method, a low frequency plasma CVD method, a high frequency (RF) plasma CVD method, a pulse wave plasma CVD method, a microwave It is various plasma CVD methods, such as plasma CVD method, Furthermore, it forms by various well-known dry processes, such as these combination.
The conditions such as the substrate temperature, gas concentration, pressure, and time during film formation are appropriately set according to the composition and film thickness of the amorphous carbon film to be formed.

  Further, if necessary, the amorphous carbon film may be a raw material gas or solid containing an element such as titanium, silicon, oxygen, nitrogen, boron, or sulfur, or an element such as titanium, silicon, oxygen, nitrogen, boron, or sulfur. A raw material (such as a target) is used in the formation process of an amorphous carbon film, or mixed and mixed, and at least one of elements such as titanium, silicon, oxygen, nitrogen, boron, and sulfur is contained in the amorphous carbon film. It may be one containing elements, or after forming an amorphous carbon film, an element such as titanium, silicon, oxygen, nitrogen, boron, sulfur, or an element such as titanium, silicon, oxygen, nitrogen, boron, sulfur is added. By using a source gas or a solid source (such as a target) containing plasma and irradiating the element with plasma, at least the surface layer of the amorphous carbon film is made of titanium, silicon, oxygen, nitrogen, boron, It may be one which contains at least one element of the elements such as.

For example, an aC: H: Si film according to an embodiment of the present invention includes an amorphous carbon film containing silicon, and the silicon content in the amorphous carbon film is 4 to 4 50 atomic percent.
Specifically, in the case of the plasma CVD method, by using a source gas containing silicon such as tetramethylsilane, methylsilane, dimethylsilane, trimethylsilane, and dimethoxydiomethylsilane, or a source gas for an amorphous carbon film An amorphous carbon film containing silicon can be formed by mixing the gas containing silicon with a hydrocarbon-based source gas such as ethylene, acetylene, or methane.

[Method of forming amorphous carbon film]
The amorphous carbon film formed on the substrate surface according to one embodiment of the present invention is ideally formed stably under a stable glow / after glow discharge in the film formation process. Actually, many arc discharges with large current locally occur due to fine dirt on the film formation substrate, electrical insulation due to oxidation of the substrate, and undulation on the surface of the substrate. When the surface of the amorphous carbon film after film formation is observed, many crater-like fine concave defects can be observed.
Amorphous carbon films are known to increase conductivity when heated in a vacuum atmosphere, and non-carbon films such as pinfalls formed at high temperatures under vacuum conditions due to arc discharge with large currents, etc. It can be assumed that the crystalline carbon defect site has high conductivity.

In addition, an amorphous carbon film is formed on a conductive metal substrate such as a stainless steel plate, and the surface on the substrate side (the surface on which the amorphous carbon film of the stainless steel plate is not formed), When the resistance of each tester (Kaise Ku-1133) was applied to the surface on which the opposing amorphous carbon film was formed and the electrical resistance was measured, an electrical resistance value of infinity (∞) was shown. However, after dropping isopropyl alcohol (IPA) having a low surface tension and high permeability by capillary action onto the same amorphous carbon film surface, the tester terminal is applied to the dropped liquid portion and electric resistance is applied. It is confirmed through a simple energization test that a resistance value of about 20 MΩ is measured and a resistance of several kΩ is confirmed when the amorphous carbon film is thin.
This is because the IPA penetrates into defects such as pin-fall of the amorphous carbon film, particularly fine concave shapes, and usually not in direct contact with the tester probe, part of which reaches the substrate, It can be estimated that this is a conductive medium that facilitates energization.

Next, the partial plating film formed on the amorphous carbon film will be described.
The partial plating film formed on the amorphous carbon film in the present invention includes various known plating methods such as electrolytic Cu plating, electrolytic Cr plating, electrolytic Sn plating, electrolytic Ni—Co alloy plating, and other alloy plating, and plating. A film can be appropriately selected.
For example, in the case where the electrolytic Ni plating according to one embodiment of the present invention is partially deposited on an amorphous carbon film, the substrate on which the amorphous carbon film is formed is made of Ni sulfamate, Ni chloride and boric acid. And is energized in a solution maintained at about 55 ° C.
This solution may contain an additive (brightening agent) as necessary. The electrolytic Ni plating layer can be formed to have a hardness of about Hv500 by adjusting the amount of additive (brightening agent) added.
Furthermore, it is also a known method to disperse fluorine resin fine particles in advance in a plating bath for electrolytic Ni plating according to an embodiment of the present invention, and to contain fluorine fine particles in the deposited Ni plating film.

The partial plating film (especially the electrolytic plating film) formed on the amorphous carbon film according to the embodiment of the present invention is a crystal defect or pinfall part on the surface of the substrate (in this case, the amorphous carbon film). It has the characteristic of forming “plating nuclei” that become the starting point of plating film growth from the surface. Also, in the pin fall part leading to the base material of the amorphous carbon film, the conductive plating solution causes pin fall due to capillary action. Since the electric field concentrates on the pinfold part with high conductivity due to the voltage applied to the plating solution part filled in the pinfall, the infinite number of layers on the amorphous carbon film surface. First, minute plating nuclei are formed in a “jumping state” in a defective portion such as pin fall scattered in the surface.
For this reason, by adjusting the conditions such as the plating time, it is possible to ensure conductivity and grow amorphous carbon such as pin fall that causes corrosion without growing a plating film on the entire surface of the amorphous carbon film. Plating nuclei can be formed in such a way that the “defects on the surface of the film” are partially, selectively, preferentially partially filled.
As a result, the amorphous carbon film laminated member according to one embodiment of the present invention can fill defects such as pinfalls with plating and improve the weather resistance of the amorphous carbon film.

In addition, the formation of the partial plating of the amorphous carbon film according to the embodiment of the present invention may be performed by various known electroplating methods that can be formed on a conductive substrate, for example, electrolytic Cu plating, electrolytic Cr plating, It can be appropriately selected and applied by various methods such as an electrolytic Ni—Co alloy plating method.
For example, the Ni plating nucleus is formed by stacking a highly corrosion-resistant hard Cr plating film on the Ni plating partially formed on the amorphous carbon film according to an embodiment of the present invention. Add a plating layer that suppresses the progress of corrosion of other plating layers, such as a tri-Ni plating layer (three-layer plating) that forms a layer of Sn-Ni alloy plating layer and has a layer containing a large amount of sulfur components. Corrosion resistance can be further improved by selecting a plurality of well-known plating methods such as stacking.

Furthermore, on the surface (upper layer portion) of the amorphous carbon film laminated member on which various partial platings according to the embodiment of the present invention are formed, the “electrical conductivity formed on the substrate (substrate)” of the present invention. It is also possible to form another film within a range that does not violate the meaning of “improvement and improvement of electric conductivity of an amorphous carbon film that is insufficient”.
For example, in the case of a component conveying member, a component aligning member, or a component storage member according to an embodiment of the present invention, specifically, an amorphous carbon film having a partially plated portion according to an embodiment of the present invention. It is also possible to impart water repellency and oil repellency to the amorphous carbon film laminated member of the present invention by additionally forming a very thin fluororesin film having a thickness of about 20 nm to 50 nm on the upper layer. In the amorphous carbon film laminated member of the present invention, the static electricity to be applied may reach a voltage of several tens of thousands of volts, and the static electricity can easily pass through a very thin fluororesin film. The thin fluororesin film formed on the convex and concave portions of the surface layer of the amorphous carbon film laminate member has poor wear resistance, and was easily worn away by contact with parts to be transported, and the fluororesin film was worn away. This is because the amorphous carbon film laminated member of the present invention is exposed at the portion.

As a further specific example, in various embodiments of the present invention, another amorphous carbon film is formed on the amorphous carbon film laminated member on which the partial plating of the present invention is formed. It is also possible to additionally form the carbon film laminated member with a thickness and physical properties that do not significantly impair the electrical conductivity, cover the partially plated portion with an amorphous carbon film, and firmly fix the plated portion.
In addition, when an amorphous carbon film laminated member in which a partial plating according to an embodiment of the present invention is formed on an electrode of a battery or the like, a battery such as conductive graphite, acetylene black, or carbon black is further formed on the upper layer portion. It is naturally planned to form a layer used as an active agent layer.
As a further specific example, in the case of forming an amorphous carbon film laminated member formed with partial plating according to an embodiment of the present invention on an electrode of a battery or the like, while further ensuring conductivity in the upper layer portion thereof, For the purpose of improving the corrosion resistance, a metal layer such as titanium or chromium having excellent corrosion resistance, a thin film layer of noble metal such as gold, platinum or rhodium, or partially plated amorphous carbon formed in the present invention Various known electroless plating layers such as electroless Ni plating, gold plating and the like can be additionally formed so as not to further promote erosion of the film.

Furthermore, it is confirmed that the plating nuclei formed on the concave defects that do not continue to the base material in advance of the amorphous carbon film grow while eroding the amorphous carbon film toward the base material side as it grows. it can.
In one embodiment of the present invention, it is composed of an amorphous carbon film containing silicon formed between a base material and an amorphous carbon film, which has a higher insulating property than a normal amorphous carbon film. The intermediate adhesion layer can be formed with a sufficient thickness necessary for the continuity of the film and the expression of the stress relaxation function in advance, without forming the intermediate adhesion layer as thin as possible in consideration of conductivity. It becomes possible.
In this case, a more insulating amorphous carbon film located between the plating nucleus to be formed and the base material is thinned by erosion of the plating, so that the plating nucleus and the base material come close to each other, and the current flows. It can be considered that it becomes easy to flow.
As described above, in one embodiment of the present invention, various “normal amorphous carbons” that could not be used because of increasing the insulation properties or were formed thinner than necessary. The range of use of the “amorphous carbon film having higher insulation than the film” can be expanded.

  Hereinafter, although the present invention is explained using an example, the present invention is not limited to these.

1. Implementation with thin amorphous carbon film Two feeders (100 mm x 100 mm, thickness 1 mm) prepared by polishing stainless steel (SUS304) to a surface roughness Ra of 0.02 μm were prepared, and the high-pressure DC pulse plasma CVD apparatus was used. Then, an amorphous carbon film was formed.
The film forming conditions were: Ar gas was adjusted to a flow rate of 30 SCCM and gas pressure of 2 Pa, plasma cleaning was performed at an applied voltage of −3 kV, Ar gas was exhausted, and trimethylsilane gas was introduced at a flow rate of 30 SCCM and gas pressure of 2 Pa. After an adhesion underlayer having a thickness of about 100 nm was formed at an applied voltage of −4 kVp, an amorphous carbon film was further formed under the following conditions.
Note that the initial arrival vacuum degree of the film forming apparatus is 7 × 10 ⁻⁴ Pa, and the pulse frequency of the high-voltage DC pulse plasma CVD apparatus pulse power supply is 10 kHz and the pulse width is 10 μs.
・ Raw material gas: Acetylene ・ Deposition gas pressure: 2 Pa
・ Gas flow rate: 30SCCM
-Applied voltage: -5 kVp
Deposition time: 15 minutes The total thickness of the formed amorphous carbon film is about 400 nm including the adhesion underlayer.

One of the amorphous carbon films formed as Example 1 was energized in a sulfamic acid Ni plating bath, and electrolytic Ni plating was performed by a known method under the following conditions. The other one not plated was used as a comparative example.
・ Current density: 1 A / dm ²
・ Plating time: 1 minute ・ Voltage: Around 2.4V

First, the surface states of Example 1 and Comparative Example were observed with a CCD camera.
FIG. 1 is a photograph taken by the CCD camera of Example 1, and (A) and (B) are magnified photographs of 500 times and 5000 times, respectively. It can be confirmed that innumerable Ni plating nuclei having a diameter of about 1 μm to 10 μm grow in a convex shape in the concave portions of the defects scattered on the surface of the amorphous carbon film.
FIG. 2 is an observation photograph (× 500) with a CCD camera of a comparative example. Many amorphous carbon film defects can be observed.
In Example 1, Ni plating nuclei grow on defective portions of the amorphous carbon film in addition to the original properties of plating nuclei where the plating nuclei grow from the defective portions on the surface of the adherend. It is considered that this is because the plating solution that penetrates into the base material or the pinfall existing at a depth to the vicinity of the base material, which is present in the crystalline carbon film, is likely to cause plating deposition in the portion.

The probe which is one of the poles of the tester is formed on the surface on the stainless steel side where the amorphous carbon film of Example 1 is not formed, and the electric resistance between the surface on which the amorphous carbon film is formed and the tester Measurement was performed by bringing the other probe into contact with a convex Ni plating nucleus. The tester used was kaise Ku-1133.
The measurement resistance values shown below are the maximum and minimum values of electrical resistance when measured by bringing a probe into contact with 10 different plating nuclei.
(1) Ni plating deposition portion Maximum resistance value: 200 kΩ Minimum resistance value: 20 kΩ
(2) Amorphous carbon film part: ∞ (infinity)
As a result of the measurement, it was confirmed that the electrical resistance drastically decreased to the level of several tens of kΩ at the Ni plating core.
From the above, it can be confirmed that the Ni plating nuclei dispersed and deposited on the amorphous carbon film is a means for ensuring electrical continuity with the stainless steel substrate through the amorphous carbon film. It was. Therefore, the material on the amorphous carbon film charged with static electricity can be grounded to the stainless steel side as the base material by contacting the Ni plating deposit.

2. Implementation with Thick Amorphous Carbon Film An amorphous carbon film was formed on a stainless steel (SUS304) base material 100 mm × 100 mm and a thickness of 1 mm using a high-pressure DC pulse plasma CVD apparatus.
The film forming conditions were as follows: the reactor reaction chamber was vacuum depressurized to 7 × 10 ⁻⁴ Pa, Ar gas was adjusted to a flow rate of 30 SCCM, gas pressure 2 Pa, plasma cleaning was performed at an applied voltage of −3 kVp, and Ar gas was After exhausting, trimethylsilane gas was introduced at a flow rate of 30 SCCM and a gas pressure of 2 Pa, an adhesion underlayer was formed at a thickness of about 200 nm at an applied voltage of −4 kVp, trimethylsilane was exhausted, and acetylene gas was supplied at a flow rate of 30 SCCM and gas After introducing an amorphous carbon film with an applied voltage of -5 kVp and a thickness of about 260 nm, the acetylene gas was further exhausted, and trimethylsilane gas was introduced again at a flow rate of 30 SCCM and a gas pressure of 2 Pa. An amorphous carbon film layer (outermost layer) containing silicon is formed at a thickness of about 200 nm at −5 kVp, and the total film thickness of the three-layer structure is To form an amorphous carbon film layer of 660 nm. The amorphous carbon film has a three-layer structure with different components because the state of the lower part of the plating nucleus formed in the amorphous carbon film (particularly, from the uppermost layer to the intermediate layer of the plating nucleus, This is because it is easy to confirm later with a SEM photograph or the like what the growth state in the lower layer] is in each layer.
Note that the frequency of the pulsed applied voltage is 10 kHz, and the pulse width is 10 μs.

The sample was energized in a sulfamic acid Ni plating bath, and known electrolytic Ni plating was performed under the following conditions to obtain Example 2.
・ Current density: 0.3 A / dm ²
・ Plating time: 1 minute ・ Voltage: Around 2.4V

The photograph which observed the surface state of Example 2 with the CCD camera is shown in FIG.
It can be confirmed that Ni plating nuclei are dispersed and deposited on the entire surface of the substrate in a nebula shape.

Next, the Ni plating nucleus part was polished in cross section including the base material and the amorphous carbon film, and the cross section (film structure of the amorphous carbon film itself) was observed.
FIG. 5 shows a cross-sectional photograph of the amorphous carbon film obtained by focused ion beam (FIB) processing of the plated deposit portion-scanning electron microscope (SEM).
The processing and observation conditions are FIB processing and secondary electron image observation. Manufacturer: Hitachi High-Technologies Corporation, Model: NB5000, Hitachi Focused Ion Beam Processing and Observation System, Acceleration Voltage: 5.0kV
WD: 5.0mm, 5.1mm, signal detector: LOWER-SE, detection signal: secondary electron,
Reflection electron elephant observation: Manufacturer: Hitachi High-Technologies Corporation, Model: NB5000, Hitachi Focused Ion Beam Processing and Observation System, Acceleration Voltage: 5.0kV, WD: 5.2mm, Signal Detector: UPPER-SE
* E × B signal processing, detection signal: backscattered electrons.

1) Processing for cross-sectional observation FIG. 4 is a diagram for explaining a processing portion for forming a cross-section by using a focused ion beam (FIB) using Example 2 as a sample. It is possible to cut the sample by hitting the focused ion beam and repelling the atoms on the sample surface. Since the focused ion beam can be narrowed from several 100 nm to several nm, fine processing becomes possible.
Select the convex part where the partial plating is deposited on the flat part of the amorphous carbon film, so that the outermost surface can be recognized at the time of cross-sectional observation. Coated.
Furthermore, a protective film (carbon film) was formed on the convex part where the Pt film was formed, which was an evaluation region.
Thereafter, focused ion beam (FIB) processing (85 μm × 12 μm) was applied to the right convex portion 1 and the left convex portion 2 in the center view.

2) State of convex section cross section The rightmost drawing of FIG. 4 is an enlarged photograph of the convex section 1, and FIG. 5 shows the state of the cross section at the broken line portion of the figure.
Each drawing shown in FIG. 5 is a photograph after the cross-section exposure (FIB processing) of the convex portion 1, and three drawings from the upper left side to the lower stage are an optical microscope secondary electron image (Lower) and a photo. Three figures from the upper right to the lower are the reflected electron images.
A depression was confirmed below the center of the convex portion 1 (upper right photo (1)).
Moreover, it can confirm that the amorphous carbon film flat part of the right side of a convex part is a 3 layer structure (lower right photograph (2)).
The distance between the center of the convex portion 1 and the substrate is close to about 100 nm.
Further, the end of the amorphous carbon film layer in which the amorphous carbon film of the three-layer structure is sequentially eroded from the upper layer to the lower layer by the deposited partial plating from the upper layer of the three-layer structure. The inclined state of the cross section can be confirmed.
Therefore, the partial plating deposition portion is not deposited so as to fill the concave portion with the original shape in the concave portion of the concave portion of the amorphous carbon film. It can be confirmed that the carbonaceous film is eroding toward the lower side.

3) State of the cross section of the convex portion 2 Although not shown, a depression is confirmed under the central portion of the convex portion 2 in the same manner as the convex portion 1 as in the case of the convex portion 1, and amorphous carbon located under the convex portion 2 In the film part, it can be confirmed that the amorphous carbon film is thin, and the distance between the central part of the convex part 2 and the substrate (the thickness of the amorphous carbon film) is close to about 100 nm as in the convex part 1. Yes.

From the above observations, the electrical conductivity of the plated deposit is high because the plating nuclei at the initial stage of plating deposition are deposited at the defects on the surface of the amorphous carbon film. It was confirmed that the amorphous carbon film was eroded with the growth of plating, and the amorphous carbon film having high insulation was thinned.
As a result, the electrical conductivity of the portion is improved, and Ni plating having high corrosion resistance is deposited on the defects inherent in the amorphous carbon film, resulting in defects in the amorphous carbon film. It is also possible to prevent deterioration of weather resistance.

Claims (7)

An amorphous carbon film laminated member having an amorphous carbon film formed on a substrate and having metal plating partially deposited on a surface layer portion and / or a defect inner wall portion of the amorphous carbon film. Te, the amorphous carbon film and the uppermost layer, the amorphous carbon film laminate member you wherein the component carrier member, a member or a component storage member for component alignment. An amorphous carbon film laminated member having an amorphous carbon film formed on a substrate and having metal plating partially deposited on a surface layer portion and / or a defect inner wall portion of the amorphous carbon film. An amorphous carbon film laminated member characterized by being an electrode. The amorphous carbon film laminated member according to claim 2, wherein the electrode is an electrode for a battery. An amorphous carbon film laminated member having an amorphous carbon film formed on a substrate and having metal plating partially deposited on a surface layer portion and / or a defect inner wall portion of the amorphous carbon film. An amorphous carbon film laminated member, which is a separator for a fuel cell. The amorphous carbon film laminated member according to any one of claims 1 to 4, wherein the amorphous carbon film contains silicon. The further amorphous carbon film is formed on the amorphous carbon film laminated member in a thickness that does not impair the electrical conductivity of the amorphous carbon film laminated member. The amorphous carbon film laminated member according to any one of 1 to 5. It is a manufacturing method of the amorphous carbon film lamination member according to any one of claims 1 to 6 ,
After the amorphous carbon film is formed on the substrate, metal plating is partially deposited on the surface layer portion and / or the defect inner wall portion of the amorphous carbon film, whereby the amorphous carbon film and the substrate are separated. A method for producing an amorphous carbon film laminated member characterized by ensuring electrical conductivity.