WO2014163038A1 - 導電部を有しケイ素を含有する非晶質炭素膜を備える構造体及びその製造方法 - Google Patents
導電部を有しケイ素を含有する非晶質炭素膜を備える構造体及びその製造方法 Download PDFInfo
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/26—Deposition of carbon only
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a structure and a manufacturing method thereof, and more particularly, to a structure including an amorphous carbon film having a conductive portion and containing silicon, and a manufacturing method thereof.
- carbon black has been used as an electrode material for a battery or the like (conducting aid for a positive electrode active material).
- acetylene black which is a kind of carbon black, has been used as an electrode material in a manganese dry battery or the like.
- carbon blacks acetylene black uses high-purity acetylene gas as a raw material, so (1) the amount of heat generated during generation is large, carbon black has relatively high crystallinity, and (2) impurities such as metals.
- the only product gas generated by pyrolysis is hydrogen, and the carbon concentration is high, so that the carbon particles are easy to collide and combine, and its intrinsic electrical resistance is ⁇ 10 -1 ⁇ It exhibits a high conductivity of about cm and is widely used as a conductive material.
- an amorphous carbon film can be easily formed on the surface of a desired substrate by a known plasma process or the like, has high hardness and excellent wear resistance, has a small friction coefficient, and prevents soft metal adhesion. It has excellent properties, and has gas barrier properties such as H 2 , H 2 O, O 2 , and ultraviolet absorption properties, Such a function can be imparted to the surface of the substrate. For this reason, amorphous carbon films have begun to be widely used in various industrial fields, mainly for feeders and carriers for small parts, trays for handling, and the like. However, although the amorphous carbon film depends on the film forming conditions and raw materials, its volume electrical resistivity is approximately 10 5 to 10 6 ⁇ ⁇ cm and exhibits insulation properties. It was difficult to use.
- an amorphous carbon film is heated by a method different from the above-described example to form a conductor portion.
- hydrocarbons are introduced into a vacuum chamber, plasma is generated, hydrocarbon radicals are deposited on the substrate, negative high voltage pulses are applied, and positive ions are accelerated to irradiate the substrate.
- a positive high voltage pulse 0.5 to 15 kV
- only the surface layer is activated in a pulsed manner and in a high temperature state.
- a highly conductive amorphous carbon film is deposited on the material (see, for example, Japanese Patent Application Laid-Open No. 2004-217975).
- a method is adopted in which the amorphous carbon film is modified to be conductive by heating.
- a general amorphous carbon film has insufficient heat resistance against heating by laser light or the like, and not only the part irradiated with laser light but also its peripheral part may be deteriorated due to heat conduction and damaged.
- the portion of the portion (wiring portion) irradiated with the laser light is drawn. If the peripheral part is altered and damaged, the quality of the electronic circuit is deteriorated. Specifically, if the peripheral portion of the portion irradiated with the laser beam is altered and becomes conductive, it becomes impossible to finely arrange the wiring.
- the conductive part is accompanied by physical friction (for example, when it is used in a contact portion with the inspection object of the contact probe), if the area around the damaged and damaged part is large, The friction resistance and wear resistance expected for the crystalline carbon film cannot be realized.
- An object of the embodiment of the present invention is to more appropriately form a conductive portion on an amorphous carbon film. Another object of the embodiment of the present invention is to improve the friction resistance, wear resistance and the like around the conductive portion of the amorphous carbon film. Other objects of the embodiments of the present invention will become apparent by referring to the entire specification.
- a raw material with low impurities such as metal high purity acetylene gas or the like
- an amorphous carbon film composed of hydrogen and carbon decomposes a hydrocarbon-based source gas such as acetylene once in a vacuum-depressurized plasma process with few impurities such as oxygen and air, and then again forms a solid It is deposited as an amorphous carbon film composed of hydrogen and carbon. It can be predicted that a carbon structure having high conductivity such as acetylene black can be obtained by heating the amorphous carbon film thus formed.
- a structure according to an embodiment of the present invention includes a base material, an amorphous carbon film containing Si, which is formed on the base material and has a conductive portion at least in part, and contains Si. Is provided.
- a contact probe according to an embodiment of the present invention includes the above-described structure, and the conductive portion of the amorphous carbon film is formed in a contact portion with an inspection object.
- a battery according to an embodiment of the present invention includes the above-described structure, and the amorphous carbon film is formed on electrodes and / or separators.
- the electronic component which concerns on one Embodiment of this invention is equipped with the structure mentioned above, and the circuit part is formed of the said electroconductive part.
- the structure manufacturing method includes a step of preparing a base material, a step of forming an amorphous carbon film containing Si on the base material, and an amorphous material containing Si. Heating the carbonaceous film to form a conductive part that has been altered to have conductivity.
- a conductive portion on the amorphous carbon film can be more appropriately formed, and friction resistance, wear resistance, etc. around the conductive portion of the amorphous carbon film can be improved.
- 2 is a photograph of the wiring formed on the base material of Example 1.
- 4 is a photograph of wiring formed on the base material of Example 2.
- FIG. 1 is a schematic diagram schematically showing a cross section of a structure 10 according to an embodiment of the present invention.
- the structure 10 according to an embodiment includes a base material 12 and a conductive portion that is formed on the base material 12 and has been modified to have conductivity by irradiation with laser light (not shown). And an amorphous carbon film 14 containing Si.
- FIG. 1 schematically represents the configuration of the structure 10 in one embodiment of the present invention, and the dimensions thereof are not necessarily shown accurately.
- the substrate 12 in one embodiment can be formed using various materials such as metal, semi-metal such as Si, resin, ceramics, and cellulose.
- the substrate 12 is made of a material having high heat resistance against laser irradiation, at least the heat resistance temperature of the amorphous carbon film 14 (about 300 ° C.), and the temperature at which the amorphous carbon film is said to become a conductor by heating ( It is preferable to use a material having a heat resistant temperature higher than about 400 ° C.).
- wet plating, dry plating (various ceramic films by plasma process or the like, conductive amorphous carbon film containing B (boron) or the like) or spray coating, resin, A coating treatment with rubber or the like may be performed.
- the shape of the substrate 12 is not particularly limited, and substrates having various shapes such as a plate shape, a planar shape, a three-dimensional solid shape, a mesh shape, a porous shape, and a film shape can be used. Further, the surface roughness of the substrate 12 is not particularly limited, and the surface roughness can be arbitrarily determined using various methods such as physical processing such as blasting and buffing, chemical etching, and electropolishing as necessary. It is also possible to modify the roughness.
- the base material 12 made of a material having a relatively low heat-resistant temperature (for example, a resin such as PET).
- a resin such as PET
- the resin film side the amorphous carbon of the base material 12
- the resin film in the portion irradiated with the laser beam is easily dissolved and extinguished, and the amorphous carbon film 14 in the same portion is irradiated with the laser beam.
- the structure 10 is similar to an interposer substrate including a portion that becomes insulating in the thickness direction (front and back direction) and a portion that becomes conductive in the same direction.
- the structure 10 can be formed.
- the amorphous carbon film 14 is formed by various methods such as a known CVD method such as a plasma CVD method and a direct current CVD method, a plasma PVD method such as a plasma sputtering method, an atmospheric pressure, and a sub-atmospheric pressure plasma method. can do.
- the amorphous carbon film 14 in one embodiment is not limited as long as it is modified to be conductive by heating such as laser light irradiation, and is an amorphous carbon film containing various different elements. It doesn't matter.
- the amorphous carbon film 14 in one embodiment is, for example, an ordinary amorphous carbon film (hereinafter simply referred to as “ordinary amorphous carbon film”) made of only hydrogen and carbon or carbon at a time before heating. It is preferable that the insulating property is higher than that in some cases. Furthermore, the amorphous carbon film 14 in one embodiment preferably has a high heat resistance against heating and a low thermal conductivity as compared with, for example, a normal amorphous carbon film. Therefore, in order to achieve high insulation, high heat resistance, or low thermal conductivity, it is preferable that the amorphous carbon film is made to contain a different element or is formed using a corresponding film formation process.
- the heat resistance of the amorphous carbon film can be improved by incorporating nitrogen into the amorphous carbon film. This is because the bond energy of the CN bond is 175 kcal / mol, whereas the bond energy of the CC bond is 145 kcal / mol, and the CN bond is more stable than the CC bond. Therefore, it is considered that the heat resistance of the film is improved.
- the amorphous carbon film 14 containing Si is formed using, for example, a plasma CVD method using tetramethylsilane, methylsilane, dimethylsilane, trimethylsilane, dimethoxydimethylsilane, tetramethylcyclotetrasiloxane, or the like as a source gas. be able to.
- the content of Si contained in the amorphous carbon film 14 is not particularly limited, but is preferably in the range of 1 to 29 atomic%, more preferably in the range of 5 to 29 atomic%. By setting the Si content to 1 atomic% or more, the internal stress of the amorphous carbon film 14 can be relaxed, and peeling from the substrate 12 can be prevented.
- the amorphous carbon film 14 containing Si in one embodiment has carbon (C), hydrogen (H), and silicon (Si) as main components, and a hydrogen (H) content of 20. It is preferable that it is ⁇ 40 atomic% and the content of silicon (Si) is 1 to 29 atomic%.
- the amorphous carbon film 14 contains Si, whereby alteration and damage in the peripheral portion of the portion irradiated with the laser light are suppressed. Further, the amorphous carbon film 14 containing Si has high heat resistance even in a portion irradiated with laser light, brittle fracture of a portion that has been changed into conductivity by the laser light, accidental peeling from the structure 10, It can be in a state in which scattering is less likely to occur. Moreover, since it is possible to suppress the fragile portion having deteriorated from being peeled off and scattered from the structure 10 during use of the structure 10, the structure 10 may become a source of contamination in the use environment or an unnecessary conductive part formation source (electricity Can be suppressed.
- the portion of the amorphous carbon film 14 in one embodiment that has been made into a conductor by irradiating it with laser light is a case where it is finely formed by fine irradiation, for example, in a honeycomb shape, a lattice shape, or a dot shape.
- a coating film is formed continuously with other parts that are not irradiated with laser light and have strong adhesion to the substrate and high fastness. For this reason, for example, compared with the case where a slurry containing acetylene black fine particles or the like is later applied to a base material or the like of a different material to form a conductive portion, the peeling of the conductive portion from the structure 10 is further suppressed. be able to.
- the amorphous carbon film 14 containing Si has a smaller alteration range due to laser irradiation than an ordinary amorphous carbon film not containing Si, the amorphous carbon film inherent in the structure 10 The unaltered part that expresses the various functions can be obtained as a wider area.
- the conductive portion made conductive by laser irradiation of the amorphous carbon film 14 in one embodiment is a hard, wear-resistant peripheral amorphous material that is not affected by laser irradiation (heating). Since the carbonaceous carbon film portion protects against external stress and the like, the durability of the structure 10 can be maintained, and the characteristics of the amorphous carbon film can be continuously imparted to the structure 10. Is possible.
- the amorphous carbon film 14 containing Si in one embodiment has low thermal conductivity as compared with a normal amorphous carbon film, it is difficult to conduct heat due to laser irradiation to the base material 12. It becomes possible to suppress the thermal deformation and damage of the base material 12 more.
- the amorphous carbon film 14 containing Si in one embodiment has a volume electrical resistivity approximately three orders of magnitude higher than that of an amorphous carbon film made of hydrogen and carbon, the amorphous carbon film Inclusion of Si in the metal strengthens the insulating property of the amorphous carbon film.
- the peripheral portion of the laser irradiation portion that is separated from the laser irradiation portion and is not directly heated is not containing Si, for example, a normal amorphous material.
- the carbon film can be left while exhibiting stronger insulation than the carbonaceous film. That is, as compared with the case of using a normal amorphous carbon film or the like, it is possible to obtain a structure 10 composed of a minimum necessary conductive portion and a stronger insulator surrounding the conductive portion.
- the electric circuit electrical wiring
- the electric circuit electrical wiring
- high voltage high withstand voltage
- the amorphous carbon film 14 containing Si in one embodiment, is changed to be conductive at an adjacent portion adjacent to the conductive portion that has been changed to have conductivity. Even in the case where there is no heat conduction portion, the oxidation of Si in the amorphous carbon film or on the surface layer proceeds, so that the insulating property of the amorphous carbon film 14 containing Si is further improved.
- a gas containing oxygen such as oxygen gas as an assist gas for the heating and melting processing process (irradiate the substrate to be processed together with the laser beam).
- the amorphous carbon film (at least Si) containing Si is further oxidized to further improve the insulation. It is known that a silicon oxide film layer such as SiO x has insulating properties, and is widely used as an insulating layer formed on a Si wafer in a semiconductor process.
- a normal amorphous carbon film containing no Si such as an electrolytic Ni plating film
- a base having poor adhesion to an amorphous carbon film such as a substrate having a strong oxidation passivated film on the surface by heating, etc.
- the adhesion to the substrate is remarkably poor, and it may not be put to practical use unless it is extremely thin.
- a stainless steel screen mesh with a severely oxidized surface formed by weaving stainless steel yarns that are heated and drawn into fiber yarns, which are used as gas permeable electrodes for fuel cells, or Ni plating or Ni alloy plating One example is a Ni plating screen mesh formed by electroforming.
- the base material has poor adhesion to the amorphous carbon film
- the amorphous carbon film is easily peeled off from the base material due to internal stress. Therefore, it is difficult to form a thick film.
- the amorphous carbon film containing Si has a smaller internal stress than the normal amorphous carbon film and has excellent adhesion to the base material, so that it can be formed as a thick film.
- SUS stainless steel
- Cr Cr
- the amorphous carbon film 14 may be a laminated film of a normal amorphous carbon film and an amorphous carbon film containing Si.
- Ordinary amorphous carbon films have poor initial adhesion and adhesion over time (sustainability of adhesion) to a substrate, particularly a metal substrate or a ceramic substrate having an oxidation passivation film on the surface layer.
- a normal amorphous carbon film has high hardness and is excellent in adhesion prevention property for soft metals.
- an amorphous carbon film containing Si has better adhesion to a metal substrate or a ceramic substrate and is superior in alkali resistance and insulation compared to a normal amorphous carbon film.
- the amorphous carbon film containing Si is inferior in hardness as compared with a normal amorphous carbon film, and the cost of the source gas or the like tends to increase.
- the amorphous carbon film 14 is formed on the amorphous carbon film containing Si as the first layer formed on the substrate 12 and the amorphous carbon film containing Si.
- a normal amorphous carbon film having a hard and soft metal adhesion prevention property is formed as the outer second layer
- an amorphous carbon film containing Si that is excellent in substrate adhesion, heat resistance, and chemical resistance will be formed, mutually complementing the advantages and disadvantages of both amorphous carbon films It can be set as a composite layer structure.
- the Raman spectra by laser Raman spectroscopy in deteriorated portions by heating including a conductive portion is between 1200 cm -1 in 1450 cm -1, between 1350 cm -1 in 1550 cm -1 , and have between 1500 cm -1 in 1650 cm -1, at least one symmetrical or asymmetrical peak of, and, from 1200 cm -1 between 1450 cm -1, and, from 1500 cm -1 to 1650 cm -1 In the case of having both peaks in between, it is preferable that the intensity of both the peaks is higher than the intensity of the peak between 1350 cm ⁇ 1 and 1550 cm ⁇ 1 .
- the Raman spectra by laser Raman spectroscopy in a portion unaltered by heating, between 1200 cm -1 in 1450 cm -1, between 1350 cm -1 in 1550 cm -1, and, between 1500 cm -1 in 1650 cm -1 has at least one symmetrical or asymmetrical peaks or shoulders, among, and between 1200 cm -1 in 1450 cm -1, and, when having peaks both between 1500 cm -1 in 1650 cm -1 Is preferably less than the intensity of the peak between 1350 cm ⁇ 1 and 1550 cm ⁇ 1 .
- the structure 10 of one embodiment is effective when applied to a use in which the conductive portion of the amorphous carbon film 14 involves physical friction.
- the structure 10 according to an embodiment in which the amorphous carbon film 14 has the above-described composite layer structure is a contact probe used in an electrical inspection device (such as an LSI probe card) for a semiconductor circuit or a printed circuit board. Application to the contact portion (contact portion) with the inspection object at the tip is very effective.
- the external electrodes of electronic components such as ceramic capacitors, inductors, and chip resistors are often made of a soft metal such as Sn plating, and the tip of the contact probe described above is extremely in contact with the contact portion with the soft metal portion. It is easy to cause adhesion.
- a normal amorphous carbon film composed of hydrogen and carbon is excellent in soft metal adhesion prevention and wear resistance, but exhibits insulation properties. It was difficult to use for the contact energization part.
- a method for improving conductivity by doping a metallic element or B (boron) or the like to an amorphous carbon film has been tried, but if a metallic element is doped, adhesion with a soft metal is likely to occur. Further, boron has a problem that it is a dangerous and expensive raw material gas.
- an amorphous carbon film doped with a metal element or boron does not have conductivity comparable to that of a metal, and its application range as a contact probe is very limited.
- the structure 10 can be applied to a contact probe by forming a conductive portion in the amorphous carbon film 14.
- the amorphous carbon film 14 has the above-described composite layer structure to the contact portion (contact portion at the tip) of the contact probe with the inspection object.
- the outer second layer ordinary amorphous carbon film
- the substrate side first layer Si-containing amorphous carbon
- the amorphous carbon film containing Si as the first layer on the substrate side is altered even if damaged. Since the damage is suppressed, the entire composite layer can be made more suitable for conductivity, adhesion to the base material, friction / abrasion resistance, and soft metal adhesion prevention.
- the laser irradiation spot is very small, such as ⁇ 10 ⁇ m to 40 ⁇ m.
- the film 14 is also effective.
- the structure (shape) of the contact probe forming the amorphous carbon film 14 for example, a roller-shaped, ring-shaped, or spherical rotating body is used instead of a needle or a protrusion, and the surface layer thereof is not a non-magnetic surface in one embodiment. It is also effective to form the crystalline carbon film 14, change a part of the crystalline carbon film 14 (to make a conductor), and disperse the contact pressure due to contact.
- the amorphous carbon film 14 containing Si, and further the amorphous carbon film 14 containing oxygen and / or nitrogen in addition to Si has a large number of hydroxyl groups derived from Si on its surface layer. It has good wettability to water and water vapor in the atmosphere, and easily forms a water film on the film under normal conditions. Further, by heating the amorphous carbon film 14 containing Si in one embodiment, the oxidation of Si also proceeds. For this reason, it becomes possible to further suppress the generation of static electricity and to improve the charge-removing property.
- the contact probe is caused by contact friction. It is possible to suppress the failure of electronic components due to static electricity and to further improve its performance.
- the structure 10 of one embodiment is also effective when applied to battery electrodes and separators.
- the amorphous carbon film is excellent in corrosion resistance, it is also considered to be used as a protective film for an electrode (for example, an aluminum electrode of an electric double layer capacitor) that is in contact with a corrosive battery electrolyte or the like, As described above, due to the fact that the amorphous carbon film exhibits insulating properties, its practical use has been difficult. In other words, when an amorphous carbon film showing insulating properties is used as a protective film for an electrode or a separator, it is necessary to form the amorphous carbon film with a thin film of about several tens of nanometers and energize it by the tunnel effect.
- amorphous carbon film is formed as a thin film, there is a problem that corrosion resistance deteriorates due to pin fall or the like.
- a normal amorphous carbon film is poor in adhesion to a substrate, and thus is easily peeled off from the substrate over time and has poor stability.
- a normal amorphous carbon film has low resistance to, for example, an alkaline solution (a white corrosion product is generated in several hours in an alkaline solution having a pH of about 10 to 12).
- an alkaline solution a white corrosion product is generated in several hours in an alkaline solution having a pH of about 10 to 12.
- a slurry is added by adding a binder or the like, applied to an electrode or separator, and dried, but the adhesion and corrosion resistance of the slurry are not sufficient, and as described above, the handling of fine particles It has the problem of adverse effects on difficulty and human body.
- a protective film having excellent adhesion and corrosion resistance can be realized. That is, a conductive part having conductivity is formed on the amorphous carbon film 14 containing Si, which is superior in adhesion and corrosion resistance to the base material compared with a normal amorphous carbon film, and used as a protective film for electrodes and separators. Therefore, it is possible to realize a battery in which the difficulty in handling fine particles such as carbon black and the adverse effects on the human body and the like are suppressed.
- the amorphous carbon film 14 in such an embodiment is formed in a thick film to suppress pin fall in the electrode or the separator to maintain the continuity of the film, and the acetylene is formed on the amorphous carbon film 14.
- a slurry of carbon black such as black, it is possible to ensure the absorption of the electrolyte solution by the high structure of carbon black.
- a battery electrode is formed by applying a carbon black slurry such as acetylene black on an aluminum foil, but the adhesion stability between the aluminum foil and a carbon black slurry such as acetylene black is known. It is very important to improve battery performance and life.
- the amorphous carbon film 14 containing Si is known to generate a large amount of functional groups such as hydroxyl groups derived from Si on its surface layer in an oxidizing atmosphere in the air or in a liquid phase. .
- the functional group formed on the surface layer of the amorphous carbon film 14 containing Si and a binder component for example, a hydroxyl group such as a coupling agent
- a binder component for example, a hydroxyl group such as a coupling agent
- acetylene black a condensation reaction
- the amorphous carbon film 14 containing Si not only improves the adhesion to the base material 12, but also is used as the uppermost layer (outermost layer) of the stacked structure of the structure 10. As a result, it is possible to easily and stably modify and protect the structure 10 by further forming a film.
- the porous body, chain or grape bunch Carbon black or the like having aggregated particles (structure structure) connected in a shape acts to suppress a change in volume of the active material, for example, interposed between active materials due to the entry and exit of lithium ions.
- the shape of the electrode can be maintained even when charging and discharging are repeated, and a conductive path can be easily secured, thereby suppressing deterioration of the battery.
- a known hydrophobic coupling agent or a fluorine-containing coupling agent that generates a functional group such as a hydroxyl group is added to the surface layer of the amorphous carbon film 14 in one embodiment to such an extent that current conduction is not inhibited (for example, 10 nm to 20 nm) as a thin protective film, and can further prevent corrosion of electrodes and separators.
- the above-described aluminum foil which is a base material for battery electrodes, naturally forms a passive insulating film such as aluminum oxide on its surface layer when handled in an oxidizing atmosphere such as in the air.
- This passive insulating film acts in a direction that impedes the conductivity (conductivity) of the electrode.
- a carbon black slurry such as acetylene black in the air, it has been difficult to prevent and suppress the oxidation of the aluminum foil described above.
- the amorphous carbon film 14 in one embodiment is formed by a vacuum process (in an environment in which the surface layer of the aluminum foil is not oxidized), before forming the amorphous carbon film 14, Ar gas or the like is formed in a vacuum.
- the amorphous carbon film 14 is continuously oxidized from the atmosphere, while the passive insulating layer on the surface of the aluminum foil is removed or thinned by the sputtering gas to stably secure the electrical conductivity of the aluminum foil itself. It can be formed as (H 2 O, O 2 gas barrier layer).
- ordinary amorphous carbon films have very poor adhesion to aluminum foil. This is because aluminum has a large coefficient of thermal expansion relative to other metals as an electrode material, and the coefficient of thermal expansion is larger than that of a normal amorphous carbon film (aluminum is large and amorphous carbon film is small). ) And hardness (aluminum is small, amorphous carbon film is large and further compressive stress is applied) is greatly deviated.
- a normal amorphous carbon film is a film of about 530 nm.
- the film may be peeled off when taken out from the vacuum apparatus.
- the amorphous carbon film 14 containing Si even a thick film of about 700 nm does not peel off when taken out from the vacuum apparatus.
- Such a phenomenon is caused by the fact that an aluminum foil that is greatly expanded by heating with plasma during the formation of the amorphous carbon film and an amorphous carbon film that is thermally expanded smaller on the aluminum foil than the aluminum foil are vacuum It is cooled when air gas is introduced (taken out) into the apparatus, and aluminum contracts rapidly.
- the amorphous carbon film expands on the aluminum foil due to compressive stress. It can be said that the aluminum foil and the normal amorphous carbon film are a combination in which peeling due to temperature change is very likely to occur.
- the aluminum foil that constitutes the electrodes of these batteries, and other metals that have a relatively large coefficient of thermal expansion compared to amorphous carbon films, and Si to stably form thick amorphous carbon films on metal alloys contain Si Although it is effective to form an amorphous carbon film, the conventional method has been difficult to apply due to its high insulating property.
- the conductive portion is formed in the amorphous carbon film 14 containing Si, so that the structure 10 can be applied as a protective film for the aluminum foil that constitutes the battery electrode.
- the amorphous carbon film 14 containing Si in one embodiment, and further, the amorphous carbon film 14 containing oxygen in addition to Si is compared with an amorphous carbon film made of normal hydrogen and carbon. Since the zeta potential on the surface becomes very negative in an acidic solution, a high performance electric double layer can be easily formed. By heating the amorphous carbon film 14 containing Si in one embodiment, it is possible to proceed with the oxidation of Si.
- an electronic component can also be formed using the structure 10 of one embodiment. That is, an amorphous carbon film 14 is formed, for example, in a planar shape on the surface layer of the insulating base material 12, and a circuit portion is drawn (formed) by laser light on the amorphous carbon film, whereby the insulating property is improved. It is possible to form an electronic component in which a circuit portion is formed as a conductive portion having conductivity on the amorphous carbon film 14 shown. In this case, the amorphous carbon film 14 containing Si has a higher insulating property than a normal amorphous carbon film and has a small range of a peripheral portion that is altered by irradiation with laser light. It is possible to form a highly integrated electronic circuit.
- an electronic circuit can also be formed using the structure 10 of one embodiment in which the amorphous carbon film 14 has the composite layer structure described above. That is, an amorphous carbon film containing Si having good adhesion to the base material and having a small range of the peripheral portion that is altered by laser light irradiation is formed on the base material 12 as the first layer, and this Si is contained. A normal amorphous carbon film is formed as a second layer on the amorphous carbon film to be processed, and a laser beam is applied to the second layer (a normal amorphous carbon film that easily changes its conductivity to the laser light). The conductive circuit portion can also be drawn by irradiating.
- the first layer (amorphous carbon film containing Si that hardly changes in quality with respect to the laser beam) can also function as an insulating layer and a substrate adhesion layer.
- Such a composite layer structure of the amorphous carbon film 14 is not limited to the above-described two-layer structure including the first layer and the second layer.
- a two-layer structure can be formed as a composite laminated structure that repeats via an insulating layer (for example, an insulating ceramic film such as SiOx or Al 2 Ox). .
- a foil obtained by oxidizing aluminum by an anodic oxidation method or the like, a film sheet obtained by applying a slurry made of a dielectric such as a glass film, ferrite or barium titanate, PET
- a layer formed of a thin film such as a metal oxide thin film or Si oxide on the surface layer of a film or the like, for example, a film formed by a plasma method, a sol-gel method, or the like is used as the insulating base material 12.
- a composite structure including a layer (amorphous carbon film containing Si) and a second layer may be used, and a composite structure including the insulating base 12 may be repeatedly stacked.
- the composite structure including at least the first layer has a conductive structure such as a new amorphous carbon film, ceramic film, metal film, insulating resin or rubber layer, and pyrrole without departing from the spirit of the present invention. It can also be set as the structure further provided with a conductive resin layer, paper, etc. It is also possible to provide a current collecting or power transmitting conductive portion at an arbitrary position of the composite structure 10 described above.
- the wiring is not formed using a plating film used for general circuit wiring or other materials such as metal. It is possible to suppress the occurrence of a short circuit of the circuit resulting from the deterioration, and it is also possible to suppress the deterioration of the circuit performance due to corrosion, alteration or the like due to oxidation.
- the amorphous carbon film 14 containing Si in one embodiment can be formed with good adhesion to a wide range of materials, for example, materials such as paper, resin, and rubber, which are difficult to perform wet plating wiring, or wet Conductive wiring and electrode portions can be applied to materials that are susceptible to element attack due to the pH of the plating bath (for example, ceramic element capacitors that cannot be plated in an acid bath).
- wiring can be performed by direct drawing with a laser beam, for example, and there is a need for a mask having a pattern opposite to that of the circuit to be formed (for example, a mask used for wiring formation by printing or wiring by etching).
- the base material 12 having a spherical surface or a three-dimensional curved surface structure, a complicated three-dimensional base material 12, and a very small base material 12 that is difficult to form wiring by masking. In addition, it is possible to appropriately form an electric circuit and wiring.
- additional layers can be formed on the amorphous carbon film 14 according to various uses and purposes.
- an amorphous carbon film may be formed as a thin film in order to protect conductive parts irradiated with laser light, a layer made of a coupling agent, a layer made of a resin adhesive, a coating film, etc.
- frictional heat reaching a certain required temperature may be used.
- the type of laser light irradiated to heat the amorphous carbon film 14 is not particularly limited as long as the amorphous carbon film 14 can be transformed into a conductive part having conductivity.
- the laser beam light source include a YAG laser, an argon laser, and an excimer laser.
- the shape of the conductive portion on the amorphous carbon film 14 formed by irradiating the laser beam is not particularly limited, and for example, a line shape, a surface shape, a dot shape, a one-stroke shape, an island shape, or 3D
- the surface layer of the base material can have various shapes such as a curved shape, a curved shape, and a linear shape inside the glass tube base material.
- the conductive portion is formed by irradiating the amorphous carbon film 14 with laser light.
- the amorphous carbon film is heated to give conductivity by a method other than laser irradiation. It is also possible.
- a step of generating a hydrocarbon plasma and depositing it on a substrate By combining the step of heating the necessary part of the amorphous carbon film by irradiating the electrons in the plasma, the necessary part of the amorphous carbon film is heated in an oxygen-free atmosphere such as in a vacuum to make the conductive amorphous
- an oxygen-free atmosphere such as in a vacuum
- the amorphous carbon film 14 is irradiated with laser light, so that only a necessary portion can be transformed into a conductor by a simple method, and the laser light is irradiated.
- the characteristics of a general amorphous carbon film are maintained, and the amorphous carbon film remains in the structure 10 as a protected portion of the modified portion from external stress or the like. Can be made.
- the heat resistance temperature of a normal amorphous carbon film is about 300 ° C., and when the amorphous carbon film is heated on a hot plate or the like under atmospheric pressure to attempt modification to conductivity, 500 ° C.
- the amorphous carbon film is crystallized and decomposed to some extent, and it is difficult to convert it into a conductor while maintaining the state of realizing the function of the amorphous carbon film.
- the structure 10 irradiates the amorphous carbon film 14 with a laser beam for a short time only in a relatively narrow and limited region (laser irradiation part) in a working environment at normal temperature and pressure. It is easy to selectively raise the temperature, and the portion having the original function as the amorphous carbon film can be relatively easily left on the amorphous carbon film 14.
- the amorphous carbon film containing Si is used to irradiate the normal amorphous carbon film formed on the substrate with laser light, thereby conducting the conductive portion.
- the friction and wear resistance, insulation, corrosion resistance, etc. in this peripheral portion can be improved,
- the conductive part on the amorphous carbon film can be formed more appropriately.
- the amorphous carbon film 14 according to the embodiment is difficult to be applied by a wet coating method (physical bonding method) in which a slurry obtained by slurrying carbon black or the like is applied to a base material and then dried and fixed. It is possible to form the material and shape on the substrate with good adhesion.
- a finer film thickness adjustment for example, adjustment in nm units
- the film thickness uniformity is also good. Become.
- Example 1 Formation of wiring (conducting part) on amorphous carbon film Hydrogen is used as a source gas on a Si (100) substrate by acetylene (having a low purity and having a purity of 98% or more) by a known plasma CVD method.
- An amorphous carbon film comprising Si and carbon having a film thickness of approximately 550 nm is referred to as Example 1, and an amorphous carbon film containing Si using trimethylsilane as a source gas by a known plasma CVD method on the same substrate was formed with a film thickness of approximately 550 nm as Example 2.
- Example 1 Frequency: 20KHz Assist gas: O 2 , oxygen content: 2 kgf / cm 2 Speed: F60 Spacing: 9 ⁇ m
- the irradiation output of the YAG laser when forming the wiring was set to “0.02W-8.87A” in Example 1-1, Example 2-1, Irradiation Examples in which the output was "0.04W-9.000A” were Example 1-2 and Example 2-2, and those in which the output was "0.10W-9.30A” were Example 1-3, Example 2-3 Examples with an irradiation output of “0.20W-9.73A” were designated as Example 1-4 and Example 2-4.
- the photographs of Examples 1-1 to 1-4 are shown in FIG.
- Example 1-1 (0.02 W), 1-2 (0.04 W), 1-3 (0.10 W), and 1-4 (0.20 W) are arranged in order from the left side to the right side of the photograph shown in FIG.
- interval of each Example is 5 mm.
- the photographs of Examples 2-1 to 2-4 are shown in FIG.
- the wirings in Example 2-1 (0.02 W), 2-2 (0.04 W), 2-3 (0.10 W), and 2-4 (0.20 W) are arranged in order from the left side to the right side of the photograph shown in FIG.
- interval of each Example is 5 mm.
- the surface state was confirmed after laser light irradiation. As a result, there was no portion where the substrate (Si) could be visually confirmed to be altered or damaged.
- the equipment used for the measurement is High precision digital multimeter 1281 manufactured by WAVETEK And the measurement environment is Temperature: 23 ⁇ 1 ° C., humidity: 50 ⁇ 5%, DC resistance is measured by a four-terminal measurement method in an electromagnetic measurement room (shield room).
- Example 1-1 2.41 k ⁇
- Example 2-1 4.13 k ⁇ 0.04 W
- Example 1-2 4.18 k ⁇
- Example 2-2 5.67 k ⁇ 0.1 W
- Example 2-3 6.11 k ⁇ 0.2 W
- Example 2-4 18.06 k ⁇
- the largest volume electric resistivity is approximately 872 ⁇ ⁇ cm
- a volume electrical resistivity of less than 1 m ⁇ ⁇ cm was confirmed, and it was confirmed that the laser beam irradiated portion was modified to have high conductivity.
- Example 1-1 and Example 2-1 As for the Raman spectra of the laser irradiated portions of Example 1-1 and Example 2-1, strong and clear Raman peaks were confirmed in the vicinity of 1330 cm ⁇ 1 (D band) and 1580 cm ⁇ 1 (G band). Such Raman peaks could not be confirmed in Example 1 (laser unirradiated) and Example 2 (laser unirradiated).
- the Raman spectra of Example 1-1 and Example 2-1 are similar to the spectrum of carbon black, and it can be estimated that conductive carbon black is generated in the film. It was also confirmed that the intensity of the Raman peak near 1330 cm ⁇ 1 (D band) was larger than the intensity of the Raman peak near 1580 cm ⁇ 1 (G band).
- Example 1-4 and Example 2-4 the Raman spectrum of the rectangular pad part that is the laser irradiation part and the laser non-irradiation part that is separated from the pad part by a fixed distance in the linear direction toward the outside of the substrate.
- the spectrum was collected, and it was confirmed which of Examples 1-4 and 2-4 had the film altered to a position farther from the laser irradiation part. Alteration status was confirmed by examining the main emergence or fluctuation of the Raman peak of 1330cm around -1 (D band) or 1580 cm -1 near (G band).
- Example 1-4 The Raman spectrum of the part not irradiated with the laser beam 8 ⁇ m away from the laser irradiation part of Example 1-4 was confirmed. A shoulder-like peak appeared in the vicinity of 1330 cm ⁇ 1 (D band), and it was confirmed that the film had started to be altered. Next, the spectrum of the part 7.8 micrometers away from the laser irradiation part was confirmed. A large peak appeared in the vicinity of 1330 cm ⁇ 1 (D band), and it was confirmed that the film was further changed. (Example 2-4) Subsequently, a Raman spectrum of a part 5 ⁇ m away from the laser irradiation part of Example 2-4 was confirmed.
- the amorphous carbon film of Example 1 is much larger than the amorphous carbon film containing Si of Example 2 in terms of the range of alteration of the film with respect to laser light irradiation, which is about three times or more as a linear distance. It could be confirmed.
- Example 1-1 and Example 2-1 the relationship between the distance from the laser irradiation part and the Raman spectrum was analyzed. It was confirmed that there was a film change point at a point 4 ⁇ m away in Example 1-1 and at a point 1.5 ⁇ m away in Example 2-1. From the above results, it can be said that Example 2 has a smaller thermal alteration range due to laser irradiation than Example 1.
- the conductive section (laser emitter), and Raman spectra by laser Raman spectroscopy in (heat affected zone in the vicinity of the laser irradiation part) conductive portion is between 1200 cm -1 in 1450 cm -1 , between 1350 cm -1 in 1550 cm -1, and has between 1500 cm -1 in 1650 cm -1, at least one symmetrical or asymmetrical peak of, and between 1200 cm -1 in 1450 cm -1, and, if it has a peak from 1500 cm -1 to both during the 1650 cm -1, the intensity of the both peaks were confirmed to be higher than the intensity of peaks between 1550 cm -1 from 1350 cm -1.
- Example 1-1 and Example 2-1 the state of the square pad part (laser irradiation part) was observed with a CCD magnified photograph. Although it was confirmed that the laser irradiated portion of Example 1-1 was all black and deteriorated, the laser irradiated portion of Example 2-1 was the same as the non-laser irradiated portion mixed in the black deteriorated portion. Many parts (parts that were not altered in appearance) could be confirmed. That is, it can be seen that Example 2 is resistant to laser irradiation and exhibits the same conductivity as Example 1.
- Example 2-1 it can be said that the portion that has not changed in appearance is in a state in which the portion that has changed into a brittle conductor formed by laser irradiation is not easily separated from the amorphous carbon film.
- the degree of damage to the amorphous carbon film caused by laser light irradiation is based on the analysis result of Example 1-1 when, for example, the results of Raman spectrum analysis of Example 1-1 and Example 1-2 are compared.
- the measurement is performed under the following conditions.
- Equipment used FE-SEM SU-70 (manufactured by Hitachi High-Tech) Measurement conditions: Acceleration voltage 5.0kV, current mode Med-High, magnification ⁇ 2000
- the oxygen atom detection amount measurement result (atomic number concentration (%)) is as follows.
- Example 1-1 1) Laser irradiation part: 35.41% 2) 2 ⁇ m laser light non-irradiated part from laser irradiated part: 6.67% 3) From the laser irradiation part 20 ⁇ m of laser light non-irradiation part: 4.09% 4) No laser irradiation: 0.7%
- Example 2-1 1) Laser irradiation part: 48.45% 2) 1 ⁇ m laser light non-irradiated part from the laser irradiated part: 21.99% 3) 3 ⁇ m laser light non-irradiated part from laser irradiated part: 5.2% 4) Laser-irradiated portion not irradiated with 20 ⁇ m laser beam: 4.62% 5) No laser irradiation: 2.43% As described above, in both Examples 1-1 and 2-1, the portion where the laser beam was irradiated and the peripheral portion thereof had a larger oxygen detection amount than that which was not irradiated with the laser beam, and oxidation progressed. It was confirmed
- Example 6 Confirmation of surface electrical resistivity What is formed by forming an ordinary carbon film of hydrogen and carbon with a film thickness of about 550 nm on a Si (100) substrate by using a known direct current pulse plasma CVD apparatus using acetylene as a source gas.
- Example 3 was obtained by forming an amorphous carbon film containing Si with trimethylsilane as a source gas with a film thickness of approximately 550 nm on the same substrate using the same plasma CVD apparatus.
- the ultimate vacuum at the time of film formation in Examples 3 and 4 the flow rate of the source gas, the gas pressure, the voltage applied to the workpiece, and the like were created under the same conditions.
- the surface electrical resistivity of Examples 3 and 4 was measured by measuring the surface resistance by the double ring method (constant voltage current measurement method).
- Measuring equipment High Resistance Meter 4339B manufactured by Agilent Technologies Resiliency cell 16008B manufactured by Agilent Technologies The main electrode size is 26 mm ⁇ , the counter electrode inner diameter is 38 mm ⁇ , the card electrode is 110 mm ⁇ 110 mm, and the load is 1 kgf.
- the measurement environment is Temperature: 23 ⁇ 1 ° C., humidity: 50% ⁇ 5%, measurement is performed in an electromagnetic measurement room (shield room).
- the measurement results of the surface resistivity at a test voltage of 10 V are 2.9 ⁇ 10 9 ⁇ / ⁇ in Example 3 and 1.6 ⁇ 10 12 ⁇ / ⁇ in Example 4, which is compared with Example 3. It was confirmed that the insulation of the material was extremely large.
- an amorphous carbon film is applied to an applied voltage of ⁇ 3 kVp, a pulse frequency of 10 kHz, a pulse width of 1 ⁇ s, and a substrate (1-1 to 1-4) and (2-1 to 2-4) on which each embodiment is formed. It was confirmed that an amorphous carbon film layer could be formed on the upper layer of the laser irradiation portion.
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Abstract
Description
本出願は、日本国特許出願2013-077182(2013年4月2日出願)に基づく優先権を主張し、この内容は参照により全体として本明細書に組み込まれる。
こうした機能を基材の表面に付与することができる。このため、非晶質炭素膜は、小型部品の搬送用フィーダやキャリア、ハンドリング用のトレイ等を中心に、多様な産業分野で広く利用され始めている。しかしながら、非晶質炭素膜は、成膜条件・原料にも依存するものの、その体積電気抵抗率が概ね105~106Ω・cm程度と絶縁性を示すため、導電性が要求される用途への使用は困難であった。
Si(100)の基板上に公知のプラズマCVD法でアセチレン(純度の低い、純度98%以上のものを敢えて使用した)を原料ガスとして水素と炭素から成る非晶質炭素膜を概ね550nmの膜厚で形成したものを実施例1とし、同じ基板上に公知のプラズマCVD法でトリメチルシランを原料ガスとしてSiを含有する非晶質炭素膜を概ね550nmの膜厚で形成したものを実施例2とした。次に、YAGレーザ(芝浦メカトロニクス製、LDP-753-8AA)を用いて、両端を四角いパット状とした長さ10mm、幅10μmのレーザ光照射配線を、実施例1、2の表層にそれぞれ形成した。レーザ光の照射条件は、以下の通りである。
周波数:20KHz
アシストガス:O2、酸素量:2kgf/cm2
速度:F60
間隔:9μm
また、実施例1及び実施例2のそれぞれに対し、配線を形成する際のYAGレーザの照射出力を「0.02W‐8.87A」としたものを実施例1-1、実施例2-1、照射出力を「0.04W‐9.00A」としたものを実施例1-2、実施例2-2、照射出力を「0.10W‐9.30A」としたものを実施例1-3、実施例2-3、照射出力を「0.20W‐9.73A」としたものを実施例1-4、実施例2-4、とした。実施例1-1~1-4の写真を図2に示す。図2に示す写真の左側から右側へ順に、実施例1-1(0.02W)、1-2(0.04W)、1-3(0.10W)、1-4(0.20W)の配線である。なお、各実施例の配線間隔は5mmである。実施例2-1~2-4の写真を図3に示す。図3に示す写真の左側から右側へ順に、実施例2-1(0.02W)、2-2(0.04W)、2-3(0.10W)、2-4(0.20W)の配線である。なお、各実施例の配線間隔は5mmである。実施例2-1~2-4については、レーザ光照射後に表面状態を確認したところ、基板(Si)が変質、損傷していることを目視レベルで確認できる部分は存在しなかった。
次に、各実施例の電気抵抗値を測定した。測定は、各試料同様に、レーザ照射部の一方端の四角いパット部と10μm幅の配線(レーザ光照射部)の接続部と、他方端レーザ照射部の四角いパット部と10μm幅の配線の接続部(レーザ光照射部)間にて行った。測定結果を以下に示す。
なお、測定に使用した装置は、
WAVETEK社製 高精度ディジタル・マルチメーター 1281
であり、測定環境は、
温度:23±1℃、湿度:50±5% 、電磁気計測室(シールドルーム)内
にて、4端子測定法により直流抵抗を測定している。
0.02W 実施例1-1:2.41kΩ、 実施例2-1:4.13kΩ
0.04W 実施例1-2:4.18kΩ 実施例2-2:5.67kΩ
0.1W 実施例1-3:6.36kΩ 実施例2-3:6.11kΩ
0.2W 実施例1-4:16.51kΩ 実施例2-4:18.06kΩ
なお、実施例1-1~1-4の内、一番大きな体積電気抵抗率は、概ね872μΩ・cmであり、実施例2-1~2-4の内、一番大きな体積電気抵抗率は、概ね996μΩ・cmであった。このように、いずれの実施例においても、1mΩ・cm未満の体積電気抵抗率が確認され、レーザ光の照射部が高い導電性に改質されていることが確認できた。
続いて、レーザ照射部からの距離とラマンスペクトルの関係を分析した。解析条件は以下の通りである。
機種名:日本分光製NRS-3300
励起波長:514.53 nm
露光時間:30 sec
グレーティング:1800 l/mm
まず、実施例1(レーザ未照射)と実施例2(レーザ未照射)及び実施例1-1、実施例2-1のそれぞれのレーザ照射部のラマン分光スペクトル解析を行った。
(実施例1-4)
実施例1-4のレーザ照射部から8μm離れたレーザ光の照射されていない部分のラマンスペクトルを確認した。1330cm-1付近(Dバンド)にショルダー状のピークが現れ、膜の変質が始まっていることが確認できた。次に、レーザ照射部より7.8μm離れた部分のスペクトルを確認した。1330cm-1付近(Dバンド)により大きなピークが現れ、さらに膜の変化が進んでいることが確認できた。
(実施例2-4)
続いて、実施例2-4のレーザ照射部より5μm離れた部分のラマンスペクトルを確認した。レーザ未照射部分とほぼ変わらない波形が確認でき、膜に変質がないことが確認できた。続いて、レーザ照射部より2.7μm離れた部分のスペクトルを確認した。若干ベースラインが右肩上がりの傾向ではあるが、1330cm-1付近(Dバンド)、1580cm-1付近(Gバンド)の変化は確認できなかった。さらに、レーザ照射部より2.6μm離れた部分のスペクトルを確認した。1580cm-1付近(Gバンド)に弱いピークが現れ、膜の変質が確認できた。以上の結果から。実施例1の非晶質炭素膜の方が実施例2のSiを含有する非晶質炭素膜よりもレーザ光照射に対する膜の変質範囲が直線距離にして3倍程度以上と非常に大きいことが確認できた。
続いて、実施例1-1と実施例2-1において、四角いパット部(レーザ照射部)の状態をCCD拡大写真にて観察した。実施例1-1のレーザ照射部は、全て黒く変質していることが確認できたが、実施例2-1のレーザ照射部は、黒く変質した部分に混在するレーザ未照射部と同様の部分(外観上は変質していない部分)が多数確認できた。即ち、実施例2はレーザ照射に対して耐性があり、且つ、実施例1と同様の導電性を発現していることが判る。実施例2-1において外観上は変質していない部分は、レーザ照射によって形成された脆い導電体に変質した部分が、非晶質炭素膜から容易に離散し難い状態となっていると言える。また、レーザ光照射による非晶質炭素膜の損傷度合いは、例えば、実施例1-1と実施例1-2のラマンスペクトル解析の結果を比較した場合、実施例1-1の解析結果が基材であるSi(100)を示す980cm-1付近のピーク強度が、1330cm-1付近(Dバンド)、1580cm-1付近(Gバンド)よりもさらに大きくなっていることが確認でき、実施例1-2の分析結果では、980cm-1付近のピーク強度が、1330cm-1付近(Dバンド)、1580cm-1付近(Gバンド)よりも大幅に小さいことからも実施例1の損傷が実施例2に比べ大きいことを同様に確認することができる。
続いて、実施例1-1、実施例2-1について、前述したラマンスペクトル解析を行った四角いパットと反対側のラマンスペクトル解析を行っていない四角パットにおける、レーザ照射部とレーザ照射部から直線方向に一定距離づつ基板の外側に向かって離れたレーザ未照射部の酸化状態を酸素原子の検出量にて確認した。また、実施例1、実施例2とそれぞれ同時に同条件で作成したSi(100)試料、実施例1(レーザ未照射)と実施例2(レーザ未照射)の測定も同様に行った。なお測定は、以下の条件で行っている。
使用機器: FE-SEM SU-70(日立ハイテク社製)
測定条件: 加速電圧 5.0kV、 電流モート゛ Med-High、 倍率 ×2000
酸素原子検出量測定結果(原子数濃度(%))は以下の通りである。
実施例1-1
1)レーザ照射部:35.41%
2)レーザ照射部から2μmのレーザ光未照射部:6.67%
3)レーザ照射部から20μmのレーザ光未照射部:4.09%
4)レーザ未照射:0.7%
実施例2-1
1)レーザ照射部:48.45%
2)レーザ照射部から1μmのレーザ光未照射部:21.99%
3)レーザ照射部から3μmのレーザ光未照射部:5.2%
4)レーザ照射部から20μmのレーザ光未照射部:4.62%
5)レーザ未照射:2.43%
このように、実施例1-1、2-1いずれもレーザ光の照射された部分、及びその周辺部が、レーザ光の照射を受けないものに対して酸素検出量が大きく、酸化が進んでいることが確認できた。
Si(100)の基板上に公知の直流パルスプラズマCVD装置でアセチレンを原料ガスとして通常の水素と炭素から成る非晶質炭素膜を概ね550nmの膜厚で形成したものを実施例3とし、同じ基板上に同じプラズマCVD装置でトリメチルシランを原料ガスとしてSiを含有する非晶質炭素膜を概ね550nmの膜厚で形成したものを実施例4とした。なお、実施例3及び4の成膜時の到達真空度、原料ガスの流量、及びガス圧、ワークへの印加電圧などは同じ条件として作成した。続いて、実施例3,4の表面電気抵抗率を2重リング法(定電圧電流測定法)による面抵抗の測定で行った。
測定装置は、
Agilent Technologies社製ハイレジスタンスメータ 4339B
Agilent Technologies社製レジスティビティ・セル16008B
主電極サイズ26mmφ、対電極内径38mmφ、カード電極110mm×110mm、荷重1kgfの条件である。
また、測定環境は、
温度:23±1℃、湿度:50%±5%、電磁気計測室(シールドルーム)内にて測定を行っている。
試験電圧10Vでの表面抵抗率の測定結果は、実施例3が2.9×109Ω/□、実施例4が1.6×1012Ω/□となり、実施例3に比べ実施例4の絶縁性が極端に大きいことが確認された。
次に、実施例の形成された基板(1-1~1-4)と(2-1~2-4)2枚の各実施例上に公知のプラズマCVD法にてさらに非晶質炭素膜を形成することができる点を確認した。DCパルスプラズマCVD装置内の試料台に実施例1、2の基板2枚を配置して1×10-3Paまで真空排気したのち、C2H2ガスを流量30SCCM、ガス圧1.5Paで導入し、印加電圧-3kVp、パルス周波数10kHz、パルス幅1μsにて非晶質炭素膜を20nm各実施例の形成された基板(1-1~1-4)と(2-1~2-4)の全面に形成し、レーザ照射部のさらに上層に非晶質炭素膜層が形成可能なことを確認した。
Claims (13)
- 基材と、
前記基材上に形成され、加熱によって導電性を有するように変質した導電部を少なくとも一部に有しSiを含有する非晶質炭素膜と、
を備える構造体。 - 前記導電部は、レーザ光の照射によって導電性を有するように変質している請求項1記載の構造体。
- 前記非晶質炭素膜は、少なくとも前記導電部に隣接する隣接部が加熱によって酸化している請求項1記載の構造体。
- 前記非晶質炭素膜は、前記導電部を含む前記加熱により変質した部分のレーザーラマン分光法によるラマンスペクトルが、1200cm-1から1450cm-1の間、1350cm-1から1550cm-1の間、及び、1500cm-1から1650cm-1の間、のうち少なくとも一つに対称又は非対称なピークを有し、かつ、1200cm-1から1450cm-1の間、及び、1500cm-1から1650cm-1の間の両方にピークを有する場合には、当該両方のピークの強度が1350cm-1から1550cm-1の間のピークの強度よりも高い請求項1記載の構造体。
- 前記非晶質炭素膜は、前記加熱により変質していない部分のレーザーラマン分光法によるラマンスペクトルが、1200cm-1から1450cm-1の間、1350cm-1から1550cm-1の間、及び、1500cm-1から1650cm-1の間、のうち少なくとも一つに対称又は非対称なピーク、あるいはショルダーを有し、かつ、1200cm-1から1450cm-1の間、及び、1500cm-1から1650cm-1の間の両方にピークを有する場合には、当該両方のピークの強度が1350cm-1から1550cm-1の間のピークの強度よりも小さい請求項1記載の構造体。
- 前記導電部は、体積電気抵抗率が1mΩ・cm未満の導電性を有する請求項1記載の構造体。
- 前記非晶質炭素膜は、前記基材上に形成されたSiを含有する第1の非晶質炭素膜と、当該第1の非晶質炭素膜上に形成されたSiを含有しない第2の非晶質炭素膜とから成る積層膜である請求項1記載の構造体。
- 前記非晶質炭素膜は、Siに加えO及び/又はNを含む請求項1記載の構造体。
- 前記非晶質炭素膜は、1-29原子%のSiを含む請求項1記載の構造体。
- 請求項1記載の構造体を備え、検査対象物との接触部に前記非晶質炭素膜の前記導電部が形成されているコンタクトプローブ。
- 請求項1記載の構造体を備え、電極及び/又はセパレータに前記非晶質炭素膜が形成されている電池。
- 請求項1記載の構造体を備え、前記導電部によって回路部が形成されている電子部品。
- 基材を準備する工程と、
前記基材上にSiを含有する非晶質炭素膜を形成する工程と、
前記Siを含有する非晶質炭素膜を加熱して導電性を有するように変質した導電部を形成する工程と、
を備える構造体の製造方法。
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JP2020153332A (ja) * | 2019-03-22 | 2020-09-24 | 日立オートモティブシステムズ株式会社 | 低熱伝導部材、低熱伝導部材の製造方法および内燃機関のピストン |
WO2021166714A1 (ja) * | 2020-02-18 | 2021-08-26 | 三菱マテリアル株式会社 | 複合伝熱部材、及び、複合伝熱部材の製造方法 |
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CN114730907A (zh) * | 2019-11-19 | 2022-07-08 | Apb株式会社 | 检查方法及组电池的制造方法 |
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