WO2020085291A1 - 炭素-金属構造体および炭素-金属構造体の製造方法 - Google Patents
炭素-金属構造体および炭素-金属構造体の製造方法 Download PDFInfo
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- WO2020085291A1 WO2020085291A1 PCT/JP2019/041284 JP2019041284W WO2020085291A1 WO 2020085291 A1 WO2020085291 A1 WO 2020085291A1 JP 2019041284 W JP2019041284 W JP 2019041284W WO 2020085291 A1 WO2020085291 A1 WO 2020085291A1
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- brazing material
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Images
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Definitions
- a carbon-metal structure and a method for producing a carbon-metal structure.
- it relates to a device including a carbon film layer containing fine carbon such as carbon nanotubes.
- Carbon nanotubes (hereinafter referred to as carbon nanotubes and CNTs; the same applies hereinafter) are applied to various devices (for example, Patent Documents 1 to 3).
- CNTs are applied, for example, to cold cathode electron emitters.
- the cold cathode electron emitter is an electron source that emits electrons into a vacuum by an external electric field, and is applied to an electron microscope, an X-ray device, an electron beam exposure device, an information display device, a lighting device, and the like.
- the cold cathode electron emitter has advantages such as low power consumption, miniaturization, fast response speed, and high electron density as compared with conventional thermionic emission.
- CNTs with high density are sparsely arranged on the emitter surface.
- CNT bundle pillar having a height of about 1 ⁇ m to 100 ⁇ m on the emitter surface in a pillar arrangement in which the ratio (H / R) of the height (H) of the pillars to the pillar spacing (R) is about 1/2. It is said that the number of pillars can be increased without weakening the electric field concentration on one pillar. Therefore, in the conventional emitter, a paste containing an organic solvent is printed in a pattern to support the CNTs. When the paste contains an organic solvent, the resistance is high and gas is released in a vacuum.
- Non-Patent Document 1 a technology is proposed in which a catalyst for forming CNTs is fixed on a heat-resistant concavo-convex substrate for growing CNTs, and CNTs are oriented and grown on the heat-resistant concavo-convex substrate to form concavities and convexities on the CNT surface according to the surface shape of the heat-resistant concavo-convex substrate.
- Non-Patent Document 1 CNTs are grown on a Si substrate to form a CNT layer.
- a CNT device can be manufactured in a short time process.
- the heat-resistant concavo-convex substrate as a mold, CNT devices having the same pattern can be manufactured, and the CNT composite tip shape can be sharpened.
- the Si substrate on which CNTs are grown has high resistance, is expensive, and is difficult to apply to products. Further, when the Si substrate is incorporated into the device, if the Si substrate is sandwiched and fixed, the Si substrate may be broken, and it is difficult to fix the CNT to the device.
- the concavo-convex shape of the CNT tip is affected by the growth of the CNTs, which may make it difficult to control the concavities and convexities.
- Non-Patent Document 2 a technique has been proposed in which CNTs grown on a Si substrate are peeled off and transferred to a copper thin film (for example, Non-Patent Document 2).
- a CNT layer having an uneven surface is formed according to the surface shape of the heat-resistant uneven substrate on which the CNT is grown.
- the heat-resistant concavo-convex substrate can be reused, and the manufacturing cost of the CNT device can be reduced.
- the CNT / Cu composite film in which a copper thin film as a current collector is directly provided on a carbon film layer containing fibrous carbon such as a CNT layer has a small thickness and is extremely difficult to handle when incorporated into a device. That is, since the CNT / Cu composite film is in the form of a film, it may be bent, lose its flatness, or be blown by the wind, and is difficult to handle. Further, when the CNT / Cu composite film is incorporated into the device, a step of cutting the CNT / Cu composite film into a required size is also necessary, which may cause operational difficulties. Although it is conceivable to form a current collector having a certain thickness in the CNT / Cu composite film, forming a current collector to a certain extent in the CNT layer increases the manufacturing cost.
- the surface of the CNT / Cu composite film connected to the device (that is, the surface of the current collector) has the same unevenness as the unevenness of the CNT layer, and the brazing property between the current collector and the device is high. May be damaged.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a technique that facilitates handling of a carbon-metal structure including a carbon film layer containing fibrous carbon.
- One aspect of the carbon-metal structure of the present invention that achieves the above object is to provide a carbon film layer containing fibrous carbon, a brazing material layer directly provided on the carbon film layer, and the carbon material through the brazing material layer. And a metal pedestal provided on the membrane layer, the carbon-metal structure.
- the carbon film layer may have irregularities with an average height of 1 ⁇ m to 100 ⁇ m and a height / spacing ratio of 1/5 to 5/1.
- the carbon film layer is a layer previously formed on a substrate
- the brazing material layer is a layer formed at an end portion of the carbon film layer opposite to the surface in contact with the substrate, Also good.
- the brazing material layer is a layer formed of a metal brazing material, and a brazing material forming the brazing material layer in the carbon film layer is impregnated at the interface between the carbon film layer and the brazing material layer.
- a mixed layer may be formed.
- the brazing material layer includes a first brazing material layer formed on the carbon film layer side and a second brazing material layer formed on the metal pedestal side and having a melting point lower than that of the first brazing material layer. It may have a multilayer structure.
- the thickness of the brazing material layer may be 1 ⁇ m or more and 50 ⁇ m or less.
- the electron emitter of the present invention which achieves the above object comprises any of the carbon-metal structures described above.
- the X-ray tube of the present invention which achieves the above-mentioned object includes the electron emitter.
- one aspect of the method for producing a carbon-metal structure of the present invention which achieves the above-mentioned object is a step of forming a carbon film layer containing fibrous carbon on a substrate and a carbon film layer formed on the substrate.
- a carbon-metal structure which includes the steps of forming a material layer, brazing a metal pedestal to the carbon film layer via the brazing material layer, and removing the substrate from the carbon film layer. It is a manufacturing method.
- the brazing material layer may include a metal brazing material vapor-deposited on the carbon film layer.
- Another aspect of the method for producing a carbon-metal structure of the present invention that achieves the above object is a step of forming a carbon film layer containing fibrous carbon on a substrate, and a carbon film layer formed on the substrate.
- the brazing material layer includes a first brazing material layer formed on the carbon film layer side and a second brazing material layer formed on the metal pedestal side and having a melting point lower than that of the first brazing material layer. It may have a multilayer structure.
- the carbon film layer may be formed on the substrate by a chemical vapor deposition method.
- the surface of the substrate may have irregularities with an average height of 1 ⁇ m to 100 ⁇ m and a height / spacing ratio of 1/5 to 5/1.
- the substrate removed from the carbon film layer may be reused as a substrate for forming the carbon film layer of another carbon-metal structure.
- a plurality of metal pedestals may be brazed to the carbon film layer via the brazing material layer.
- the carbon-metal structure including the carbon film layer containing fibrous carbon. Further, it is possible to provide a carbon-metal structure which has less degassing, low resistance, and high emission performance.
- 3B is a view for explaining before and after brazing of the CNT device of Example 1 (thickness of brazing material layer: 3.3 ⁇ m), and (b) is a SEM image of the CNT layer surface of the same CNT device.
- A A schematic view of an apparatus for evaluating the electrode characteristics of the CNT device, and (b) a characteristic view showing the electrode characteristics (IV characteristics) of the CNT device of Example 1 (thickness of brazing material layer: 3.3 ⁇ m).
- (C) is a characteristic diagram showing electrode characteristics (cycle characteristics) of the same CNT device. It is a figure explaining the outline of the CNT device of Example 2, (a) The figure before brazing, (b) The figure after brazing.
- FIG. 9 is a diagram illustrating an outline of a CNT device of Example 4.
- 9 is a SEM image of the CNT layer surface of the CNT device of Example 4.
- 16 is a characteristic diagram showing electrode characteristics (IV characteristics) of the CNT device of Example 4.
- FIG. 7 is a characteristic diagram showing electrode characteristics (cycle characteristics) of the CNT device of Example 4.
- FIG. 10 is a diagram illustrating an outline of a CNT device of Example 5.
- 9 is a SEM image of the CNT layer surface of the CNT device of Example 5.
- 11 is a characteristic diagram showing electrode characteristics (IV characteristics) of the CNT device of Example 5.
- FIG. 9 is a characteristic diagram showing electrode characteristics (IV characteristics after 100 cycles) of the CNT device of Example 5, and (b) a characteristic diagram showing electrode characteristics (cycle characteristics) of the CNT device of Example 5.
- FIG. 9 is a diagram illustrating an outline of a CNT device of Example 6. It is explanatory drawing explaining the other example of the manufacturing process of the CNT device which concerns on embodiment of this invention.
- FIG. 10 is a diagram illustrating an outline of a CNT device of Example 7. It is a figure explaining the CNT device of a comparative example.
- FIG. 10 is a diagram illustrating an outline of a CNT device of Example 8.
- a carbon-metal structure according to an embodiment of the present invention a method for manufacturing a carbon-metal structure, and an electron emitter and an X-ray tube including the carbon-metal structure according to an embodiment of the present invention will be described in detail with reference to the drawings.
- the carbon-metal structure is not limited to the embodiment. It can be applied to a device to which fine carbon is applicable, such as an electrode of an electric double layer capacitor.
- the carbon film layer constituting the carbon-metal structure includes not only a layer containing CNT but also a layer in which a large number of protrusions made of carbon containing fibrous carbon such as string-like or needle-like are spread out in a plane. Just do it. Further, the carbon film layer is more preferably a layer including a region in which fibrous carbon is arranged in a state of standing in the thickness direction of the film.
- the CNT device 1 includes a CNT layer 2, a brazing material layer 3, and a metal pedestal 4.
- a mixed layer 5 is formed between the CNT layer 2 and the brazing material layer 3 and the brazing material forming the brazing material layer 3 is impregnated at the end of the CNT layer 2.
- the CNT layer 2 is composed of, for example, CNTs formed on the catalyst 7 carried on the heat-resistant concavo-convex substrate 6.
- the heat-resistant uneven substrate 6 and the catalyst 7 will be described later in detail with reference to FIG.
- Concavities and convexities corresponding to the concavo-convex surface of the heat-resistant concavo-convex substrate 6 are formed on the surface of the CNT layer 2.
- a CNT bundle pillar having an average height of 1 ⁇ m to 100 ⁇ m is formed on the emitter surface with a ratio (H / R) of pillar height (H) to pillar spacing (R) of 1 /
- a pillar arrangement of 5 to 5/1 is preferable.
- the average height of the pillars is obtained by, for example, observing the cross section of the emitter with a scanning electron microscope or observing the surface with a laser microscope to obtain the height distribution of the pillars, and determining the height of 10 pillars
- the number of pillars is calculated by calculating the average height of the pillars.
- the size and density of the CNT bundle pillars are selected according to the electric field concentration of the CNTs and the life of the CNT layer 2. Therefore, the heat-resistant concavo-convex substrate 6 has concavities and convexities having an average height of 1 ⁇ m to 100 ⁇ m and a height / spacing ratio of 1/5 to 5/1.
- This average height is obtained by the same method as the average height of the pillars of the CNT layer 2.
- the interval between the irregularities is small. Therefore, the interval between the irregularities is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less. Further, in order to enhance the concentration of the electric field on the emitter, it is preferable that the interval between the irregularities is large. Therefore, the interval between the irregularities is preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more.
- the CNT forming the CNT layer 2 may be a single layer or a multi-layer, and the diameter of the CNT is preferably 30 nm or less.
- the brazing material layer 3 is formed of a brazing material that joins the CNT layer 2 and the metal pedestal 4.
- the brazing material may be any brazing material having a melting point lower than that of the metal pedestal 4, and a suitable brazing material is appropriately selected according to the type of the metal pedestal 4.
- a metal brazing material such as silver (Ag) or an alloy of silver (Ag) and copper (Cu) (Ag—Cu alloy) is preferably used for the metal pedestal 4 of copper (Cu).
- the ratio of Ag to Cu may be any.
- an additive element such as tin (Sn) or indium (In), or nickel for improving the wettability of the metal brazing material (for example, silver brazing material). It may contain additional elements such as (Ni), manganese (Mn), and palladium (Pd).
- a mixed layer 5 for example, a mixed layer of 1 ⁇ m or less in which the brazing material layer 3 is soaked in the CNT layer 2 is formed.
- the thickness of the brazing material layer 3 is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more. This is because if the thickness of the brazing material layer 3 is less than 1 ⁇ m, the bonding between the CNT layer 2 and the metal pedestal 4 may be poor, and the transfer of the CNT layer 2 may be difficult. On the other hand, when the thickness of the brazing filler metal layer 3 is more than 50 ⁇ m, the CNTs are filled with the brazing filler metal during brazing, which may make it difficult to peel the CNT layer 2 from the heat-resistant concavo-convex substrate 6 for growing the CNT layer 2. is there. Moreover, the CNT pillars transferred to the metal pedestal 4 may be buried in the brazing material.
- the thickness of the brazing material layer 3 is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and further preferably 10 ⁇ m or less.
- the thickness of the brazing material layer 3 can be obtained, for example, by dividing the mass of the brazing material per unit area (g / cm 2 ) by the true density of the brazing material (g / cm 3 ).
- the brazing material layer 3 is not limited to a single layer structure, and may have a multi-layer structure (for example, a two-layer structure having first and second brazing material layers 31 and 32 in FIG. 23 described later). Alternatively, different metal brazing materials may be applied to the respective layers.
- the metal pedestal 4 is a metal member having conductivity.
- the metal pedestal 4 is preferably a metal member containing any one or more of copper, tin, zinc, aluminum, magnesium, titanium, iron, cobalt, nickel, chromium, and silver.
- the metal pedestal 4 preferably has a rigidity that facilitates handling when the CNT device 1 is incorporated into the apparatus, and for example, a metal member having a thickness of 0.02 mm to 10 mm is used.
- the cylindrical metal pedestal 4 is used, but a metal member having any shape such as a plate shape, a column shape, a cone shape, and a hemispherical shape is used.
- the metal pedestal 4 it is not necessary that all of the metal pedestal 4 is made of metal as long as it has a conductor layer on the surface to which the CNT layer 2 is brazed.
- the heat-resistant substrate 6 ′ may be any substrate as long as it has heat resistance, and for example, a substrate made of ceramic, quartz glass, alumina sintered body, SiC sintered body, high heat-resistant alloy, Inconel, stainless steel, or the like is used. In particular, a silicon substrate, a quartz glass substrate, or the like, which is easily available as a high-purity product, is generally used.
- the texture can be formed by mechanical cutting or chemical etching of the surface of the heat resistant substrate 6 ′.
- the heat-resistant uneven substrate 6 can be obtained by forming a texture by anisotropically etching with an alkaline solution such as NaOH aqueous solution.
- an alkaline solution such as NaOH aqueous solution.
- a regular pyramid-like texture is obtained on a single crystal silicon substrate, and a random-shaped texture is obtained on a polycrystalline silicon substrate.
- a catalyst 7 for CNT generation is supported on the heat-resistant concavo-convex substrate 6 (STEP 2).
- the catalyst 7 is carried on the heat-resistant concavo-convex substrate 6 by, for example, RF magnetron sputtering. Iron (Fe), cobalt (Co), nickel (Ni), molybdenum (Mo), or the like is used as a catalyst substance that produces CNTs.
- a carrier layer 8 for example, aluminum oxide (Al), magnesium oxide (Mg), etc.
- the average film thickness of the catalyst 7 preferably has a film thickness (for example, 0.1 nm to 5 nm) that provides a catalyst particle size that is optimum for CNT growth.
- the CNT is synthesized by, for example, a chemical vapor deposition method (Chemical Vapor Deposition, CVD).
- the carbon source include hydrocarbons such as methane, ethylene and acetylene, carbon monoxide, and alcohols such as ethanol and methanol.
- the reaction conditions of the CVD method for example, the temperature is selected from the range of 600 ° C. to 1200 ° C., the pressure is selected from the range of 0.001 atm to 1 atm, and the reaction time is usually selected from the range of 1 second to 1 hour.
- the CNTs are formed in a state of being in contact with the heat-resistant concavo-convex substrate 6 and oriented substantially perpendicular to the surface of the heat-resistant concavo-convex substrate 6.
- the number density of CNTs growing on the catalyst 7 can be controlled by the amount of the catalyst 7 supported. Note that not only the number distribution of CNTs growing on the heat-resistant concavo-convex substrate 6 but also the diameter and number of layers of CNTs, the thickness of many grown CNT bundles, the degree of entanglement, and the like change depending on the amount of catalyst 7 supported.
- the brazing material layer 3 is formed on the CNT layer 2 (STEP 4).
- the brazing material layer 3 is formed by, for example, co-evaporation or sputtering of a substance forming the brazing material.
- Ag—Cu is used as a brazing material
- Ag having a high vapor pressure is preferentially evaporated, and a brazing material having a high Ag ratio is deposited on the CNT layer 2.
- a composition gradient film in which the proportion of Cu is gradually increased is formed.
- a brazing material adjusted to a predetermined composition ratio may be used, or an individual metal material may be used as a raw material to form the brazing material layer 3 having a predetermined composition ratio.
- the brazing material layer 3 may be provided on the metal pedestal 4 side.
- the brazing material layer 3 having a composition gradient opposite to that when the brazing material layer 3 is provided on the CNT layer 2 is formed.
- the brazing material layer 3 is formed by sputtering which evaporates an element regardless of the vapor pressure, or when the brazing material layer 3 is formed by vapor deposition using a plurality of vapor deposition sources using individual metal materials as raw materials, the composition is A brazing material layer 3 having no inclination is formed.
- the composition of the brazing material layer 3 to be vapor-deposited may be different from the composition of the brazing material layer 3 of the final device. For example, when Ag is vapor-deposited on the CNT layer 2 as a brazing material, when brazing is performed on the Cu metal pedestal 4, Cu and Ag are mixed to form a brazing material layer 3 containing an Ag—Cu alloy.
- the metal pedestal 4 is brazed to the CNT layer 2 (STEP 5). Brazing is performed by heating to a temperature at which the brazing material of the brazing material layer 3 melts.
- the melting point of the Ag-Cu alloy is 779 ° C, so it is preferable to heat the material to 779 ° C or higher for brazing, and when using another brazing material, the brazing material is used. The brazing temperature is adjusted according to the melting point of.
- the timing for cutting the CNT device 1 into an arbitrary size may be before or after peeling the heat-resistant concavo-convex substrate 6.
- the brazing material layer 3 is formed on the entire surface of the CNT layer 2 and the metal pedestal 4 is brazed and the heat-resistant concave-convex substrate 6 is peeled off, when the brazing material layer 3 is thin, the brazing material layer 3 and the CNT layer 2 are the metal pedestal. It is automatically cut and transferred according to the shape of 4.
- the brazing material layer 3 when the brazing material layer 3 is as thin as about 1 ⁇ m to 5 ⁇ m, it is transferred in the shape of the metal pedestal 4, and when the brazing material layer 3 is as thick as 10 ⁇ m or more, the entire brazing material layer 3 is peeled off from the heat-resistant uneven substrate 6. , Is also transferred around the metal pedestal 4. Further, when the brazing material is vapor-deposited on the CNT layer 2, if the brazing material layer 3 is formed in a pattern using a mask, the CNT layer 2 adheres only to the metal pedestal 4 and is adhered to other parts of the CNT layer 2.
- the brazing material layer 3 does not exist, only the pattern portion of the CNT layer 2 is transferred to the metal pedestal 4 when the metal pedestal 4 and the heat-resistant concavo-convex substrate 6 are separated. Good cut automatically. Also, by forming the brazing material layer 3 on the metal pedestal 4, the CNT layer 2 is automatically cut according to the shape of the metal pedestal 4. Furthermore, when a plurality of metal pedestals 4 are brazed to the CNT layer 2 and the heat-resistant concavo-convex substrate 6 and the metal pedestal 4 are separated, the CNT layer 2 is formed whether the brazing material layer 3 is formed on the entire surface or in a pattern. Are automatically cut according to each metal pedestal 4.
- Examples 1 to 7 relate to the CNT device manufactured based on the manufacturing method shown in FIG. 2, and show the observation result, evaluation result, etc. of each CNT device.
- Example 1 of the present invention CNT devices 1a and 1b applicable to the emitter of the X-ray apparatus were manufactured by the CNT device manufacturing method (FIG. 2) according to the embodiment of the present invention.
- a Si substrate was used as the heat-resistant concavo-convex substrate 6
- a copper pedestal with a diameter of 6 mm and a thickness of 4.5 mm was used as the metal pedestal 4
- an Ag—Cu alloy was used as the brazing material.
- Fe was used for the catalyst 7
- AlO x was used for the carrier layer 8.
- a Si substrate whose surface was ground with sandpaper was treated with hydrofluoric acid to remove SiO 2 .
- a texture of 5 ⁇ m to 10 ⁇ m was formed by anisotropic etching for 30 minutes in a 2 wt% NaOH / 20 vol% isopropyl alcohol aqueous solution at 80 ° C. (STEP 1).
- Fe 4 nm / Al 15 nm was carried on the surface of the Si substrate by using RF magnetron sputtering (STEP 2). Al was oxidized to AlO x when it contacted with air.
- the brazing material layers of the CNT devices 1a and 1b were controlled by changing the charged amounts of Ag and Cu of the vapor deposition source, and vapor deposition was carried out until the Ag and Cu of the vapor deposition source were exhausted.
- the vapor deposition times of the CNT devices 1a and 1b were 60 seconds and 30 seconds, respectively, and the thickness of the brazing material layer 3 was 10.6 ⁇ m and 3.3 ⁇ m, respectively.
- the metal pedestal 4 was provided on the brazing material layer 3, and the metal pedestal 4 was brazed to the CNT layer 2 by heating for 5 minutes (CNT device 1a) or 11 minutes (CNT device 1b) under the conditions of 780 ° C. and Ar 10 Torr ( STEP 5). As shown in FIGS. 3 and 4, in each of the CNT devices 1 a and 1 b, the CNT layer 2 was peelable, and the CNT layer 2 was transferred to the metal pedestal 4. However, when manufacturing the CNT devices 1a and 1b, the uniform CNT layer 2 may not be transferred to the entire surface of the metal pedestal 4, and there is a problem with reproducibility.
- FE performance field emission performance
- the FE performance evaluation was performed using the CNT device 1b as the cathode and the glass substrate 9 with the ITO film (tin oxide-doped indium oxide film) as the anode. Quartz glass having a thickness of 500 ⁇ m is used as a spacer 10 and they are opposed to each other, and a current value is measured when a sweep voltage of 0 to 1000 V is applied for 100 cycles in a vacuum of 10 ⁇ 5 Pa to obtain the FE characteristics of the CNT device 1 b. The life was evaluated. As shown in FIGS.
- an emission current of 2.5 mA or more (area: 0.28 cm 2 , current density: 8.8 mA / cm) at an electrode distance of 500 ⁇ m, an applied voltage of 1000 V, that is, an electric field strength of 2 V / ⁇ m. 2 or more) was stably obtained, and the CNT device 1b had excellent characteristics and life as an emitter.
- Example 2 In Example 2, a CNT device 11 having an Ag—Cu brazing material layer thickness of 26.7 ⁇ m was manufactured.
- a Si substrate was used as the heat-resistant concavo-convex substrate 6, and a copper pedestal having a diameter of 6 mm and a thickness of 4.5 mm was used as the metal pedestal 4.
- the detailed description of the same steps as the first embodiment (STEP1 to STEP3) is omitted (the same applies to the third to seventh embodiments).
- STEP 1 to STEP 3 were performed in the same manner as in Example 1 except that the annealing during CNT synthesis was 3 minutes and the C 2 H 2 partial pressure was 0.5 Torr, and CNT was synthesized on the Si substrate. Then, Ag and Cu were co-evaporated on the CNT grown on the Si substrate for 75 seconds to form a brazing material layer 3 (Ag-Cu brazing material layer) on the surface of the CNT layer 2 (STEP 4).
- the metal pedestal 4 was provided on the brazing material layer 3, and the metal pedestal 4 was brazed to the CNT layer 2 by heating for 5 minutes under the conditions of 800 ° C. and Ar 10 Torr (STEP 5). After brazing, the metal pedestal 4 was peeled off from the Si substrate (heat-resistant concavo-convex substrate 6) to manufacture the CNT device 11 of Example 2 (STEP 6).
- the CNT layer 2 was transferred onto the metal pedestal 4 (see the upper right figure in FIG. 6B).
- the Ag—Cu film around the metal pedestal 4 adhered to the side surface of the metal pedestal 4 (see the upper left, lower left, and lower right of FIG. 6B). Further, since the CNT layer 2 was peeled from the heat-resistant concavo-convex substrate 6, the substrate surface of the peeled heat-resistant concavo-convex substrate 6 was exposed (see the upper left diagram of FIG. 6B).
- Example 3 In Example 3, a CNT device 12 having an Ag brazing material layer thickness of 35.3 ⁇ m was manufactured. In this example, the CNT device 12 was manufactured in the same manner as in Example 2 except that the type of brazing material was different.
- CNTs were synthesized on a Si substrate by the same method as in STEP 1 to STEP 3 of Example 2. Then, Ag is deposited for 40 seconds in vacuum (for example, 10 ⁇ 4 Pa) on the CNTs grown on the Si substrate to form a brazing material layer 3 (Ag brazing material layer) on the surface of the CNT layer 2. (STEP 4).
- the metal pedestal 4 was provided on the brazing material layer 3, and the metal pedestal 4 was brazed to the CNT layer 2 by heating for 5 minutes under the conditions of 800 ° C. and Ar 10 Torr (STEP 5). After brazing, the metal pedestal 4 was peeled off from the Si substrate (heat-resistant concavo-convex substrate 6) to manufacture the CNT device 12 of Example 3 (STEP 6).
- the CNT layer 2 was transferred onto the metal pedestal 4 (see the upper right figure in FIG. 7B).
- the Ag film around the metal pedestal 4 was attached to the side surface of the metal pedestal 4 (see the upper left, lower left, and lower right of FIG. 7B). Further, since the CNT layer 2 was peeled from the heat-resistant concavo-convex substrate 6, the substrate surface of the peeled heat-resistant concavo-convex substrate 6 was exposed (see the upper left diagram of FIG. 7B).
- Example 4 In Example 4, three CNT devices 13a to 13c having different brazing times were produced.
- CNT devices 13a to 13c were manufactured by the same method as in Example 1 except that the thickness of the brazing material layer, the brazing temperature and the brazing time were different.
- CNTs were synthesized on a Si substrate by the same method as in STEP 1 to STEP 3 of Example 1. Then, Ag and Cu are co-deposited on the CNTs grown on the Si substrate in a vacuum (for example, 10 ⁇ 4 Pa) for 30 seconds, and the brazing filler metal layer 3 (Ag—Cu solder) is formed on the surface of the CNT layer 2. Material layer) was formed (STEP 4). The thicknesses of the brazing material layer 3 of the CNT devices 13a to 13c were 3.6 ⁇ m, 3.4 ⁇ m, and 3.5 ⁇ m, respectively.
- the metal pedestal 4 is provided on the brazing material layer 3, and the metal pedestal 4 is brazed to the CNT layer 2 by heating at 800 ° C. and Ar 10 Torr for 5 minutes, 3 minutes or 1 minute ( STEP 5). After brazing, the metal pedestal 4 was peeled off from the Si substrate (heat-resistant concavo-convex substrate 6) to manufacture the CNT devices 13a to 13c of Example 4 (STEP 6).
- the CNT layer 2 was transferred onto the metal pedestal 4 by peeling off the metal pedestal 4 in each of the CNT devices 13a to 13c.
- the Ag—Cu film and the CNT layer 2 outside the contact surface of the metal pedestal 4 were not transferred to the metal pedestal 4 and remained on the surface of the heat-resistant concavo-convex substrate 6. Further, since the CNT layer 2 was peeled off from the heat-resistant concavo-convex substrate 6 in the shape of the metal pedestal 4, the substrate surface of the portion corresponding to the metal pedestal 4 was exposed in the peeled heat-resistant concavo-convex substrate 6.
- the FE performance evaluation was performed using any of the CNT devices 13a to 13c as the cathode and the glass substrate 9 with the ITO film as the anode (see FIG. 5 (a)).
- the quartz glass having a thickness of 500 ⁇ m is used as a spacer 10 and they are opposed to each other, and the current value is measured when a sweep voltage of 0 to 1000 V is applied for 100 cycles in a vacuum of 10 ⁇ 5 Pa to measure the FE of the CNT devices 13a to 13c.
- the characteristics and life were evaluated.
- the CNT device 13b had the best results as the emitter characteristics.
- the brazing conditions temperature and time
- the brazing temperature and time are appropriately adjusted according to the melting point of the brazing material.
- Example 5 In Example 5, three CNT devices 14a to 14c having different Ag-Cu brazing material layer thicknesses were manufactured.
- CNTs were synthesized on a Si substrate by the same method as in STEP 1 to STEP 3 of Example 4. Then, Ag and Cu are co-deposited on the CNTs grown on the Si substrate in a vacuum (for example, 10 ⁇ 4 Pa), and the brazing material layer 3 (Ag—Cu brazing material layer) is formed on the surface of the CNT layer 2. ) Was formed (STEP 4).
- the vapor deposition times of the brazing material layer 3 of the CNT devices 14a to 14c were 20 seconds, 40 seconds and 50 seconds, respectively, and the thicknesses thereof were 1.3 ⁇ m, 4.8 ⁇ m and 12.5 ⁇ m, respectively.
- the metal pedestal 4 was provided on the brazing material layer 3, and the metal pedestal 4 was brazed to the CNT layer 2 by heating for 1 minute under the conditions of 800 ° C. and Ar 10 Torr (STEP 5). After brazing, the metal pedestal 4 was peeled off from the Si substrate (heat-resistant concavo-convex substrate 6) to manufacture the CNT devices 14a to 14c of Example 5 (STEP 6).
- FIG. 13 shows surface SEM images of the CNT layer 2 of the CNT devices 14a to 14c.
- the brazing material layer 3 and the CNT layer 2 were transferred in the shape of the metal pedestal 4, but the brazing material exuded on most of the surface of the CNT layer 2. From this, it is considered that the brazing material may be easily absorbed by the CNT layer 2 as the brazing material layer 3 becomes thinner.
- the CNT layer 2 has the shape of the metal pedestal 4 and is uniformly transferred onto the entire surface of the metal pedestal 4.
- the square CNT layer 2 is transferred to the metal pedestal 4 in a state where the brazing material layer 3 is vapor-deposited, and a part of the CNT layer 2 (and the brazing material layer 3) is It was transcribed so as to cling to the surroundings. That is, in the CNT device 14c, the entire brazing material layer 3 was transferred to the metal pedestal 4. Then, a part where the brazing filler metal exudes was observed on the surface of the transferred CNT layer 2. From this, it is considered that when the thickness of the brazing filler metal layer 3 increases, the brazing filler metal becomes excessive and a part of the brazing filler metal may exude to the surface of the CNT layer 2.
- FIG. 14 and 15 show the FE performance evaluation results of the CNT devices 14a to 14c. Similar to the FE performance evaluation of Example 1, the FE performance evaluation was performed by using any of the CNT devices 14a to 14c as the cathode and the glass substrate 9 with the ITO film as the anode (see FIG. 5 (a)). . Quartz glass having a thickness of 500 ⁇ m is used as a spacer 10 and they are opposed to each other, and the current value is measured when a sweep voltage of 0 to 1000 V is applied for 100 cycles in a vacuum of 10 ⁇ 5 Pa to measure the FE of the CNT devices 14 a to 14 c. The characteristics and life were evaluated.
- the CNT device 14a was confirmed by SEM to have a good performance of about 1.1 mA, although the exudation on the surface of the brazing material was confirmed in most of the cases.
- the CNT device 14b maintained a good performance even after 100 cycles, although a large current initially flowed and the current amount decreased thereafter.
- the FE performance of the CNT device 14c was about 0.27 mA, which was lower than that of the other CNT devices 14a and 14b.
- Example 6 In Example 6, two CNT devices 15a and 15b having different brazing temperatures and brazing times were produced.
- CNTs were synthesized on a Si substrate by the same method as in STEP 1 to STEP 3 of Example 4. Then, Ag and Cu are co-deposited on the CNTs grown on the Si substrate in a vacuum (for example, 10 ⁇ 4 Pa), and the brazing material layer 3 (Ag—Cu brazing material layer) is formed on the surface of the CNT layer 2. ) Was formed (STEP 4).
- the vapor deposition times of the brazing material layer 3 of the CNT devices 15a and 15b were 20 seconds and 30 seconds, respectively, and the thicknesses thereof were 1.2 ⁇ m and 1.0 ⁇ m, respectively.
- a metal pedestal 4 was provided on the brazing filler metal layer 3, and the metal pedestal 4 was brazed to the CNT layer 2.
- the CNT device 15a was heated and brazed for 5 minutes at 820 ° C. and Ar 10 Torr, and the CNT device 15b was heated and brazed for 30 minutes at 800 ° C. and Ar 10 Torr (STEP 5).
- the metal pedestal 4 was peeled off from the Si substrate (heat-resistant concavo-convex substrate 6) to manufacture the CNT devices 15a and 15b of Example 6 (STEP 6).
- the brazing material slightly exuded on the surface of the CNT layer 2, but the CNT layer 2 was transferred in the shape of the metal pedestal 4.
- Example 7 As shown in FIG. 17, the CNT devices 16a and 16b of Example 7 are obtained by arranging a plurality of metal pedestals 4 on the brazing material layer 3 on the CNT layer 2 and brazing the CNT layer 2 to the metal pedestal 4. Is.
- CNTs were synthesized on a Si substrate by the same method as in STEP 1 to STEP 3 of Example 4. Then, Ag and Cu are co-deposited on the CNTs grown on the Si substrate in a vacuum (for example, 10 ⁇ 4 Pa), and the brazing material layer 3 (Ag—Cu brazing material layer) is formed on the surface of the CNT layer 2. ) Was formed (STEP 4).
- the vapor deposition times of the brazing material layer 3 of the CNT devices 16a and 16b were 30 seconds and 40 seconds, respectively, and the thicknesses thereof were 4.8 ⁇ m and 4.5 ⁇ m, respectively.
- a plurality of metal pedestals 4 were provided on the brazing filler metal layer 3, and the CNT layer 2 was brazed to the CNT layer 2 by heating for 1 minute under the conditions of 800 ° C. and Ar 10 Torr (STEP 5). After brazing, the metal pedestal 4 was peeled off from the Si substrate (heat-resistant concavo-convex substrate 6) to manufacture the CNT devices 16a and 16b of Example 7 (STEP 6).
- the brazing material layer 3 was automatically cut into the shape of the metal pedestal 4, and the CNT layer 2 was transferred on the metal pedestal 4 in accordance with the shape of the metal pedestal 4.
- the brazing material was slightly exuded on the surface of the CNT layer 2.
- the CNT layer 2 was transferred onto the entire surface of the metal pedestal 4 without being uniformly projected. No exudation of the brazing material was confirmed on the surface of the CNT layer 2.
- Table 1 shows the brazing conditions of Examples 1 to 7 and the FE performance evaluation results.
- the thickness of the brazing filler metal layer 3 is 1 ⁇ m to 50 ⁇ m, preferably 3 ⁇ m to 10 ⁇ m, and the temperature is 780 ° C. to 820 ° C.
- the time can be selected within 30 minutes.
- a current collector (copper thin film 18) is directly provided on the surface of the CNT layer 2.
- a Si substrate whose surface was ground with sandpaper was treated with hydrofluoric acid to remove SiO 2 .
- the surface of the Si substrate was etched for 30 minutes in a 2 wt% NaOH / 20 vol% isopropyl alcohol aqueous solution at 80 ° C. to form a texture of 5 ⁇ m to 10 ⁇ m.
- Fe 4 nm / Al 15 nm was carried on the surface of the Si substrate by using RF magnetron sputtering.
- Cu was vapor-deposited in a vacuum (for example, 10 ⁇ 4 Pa) for 1 minute to form a copper thin film 18 on the surface of the CNT layer 2. Then, the copper thin film 18 was peeled off from the Si substrate to fabricate a CNT device 17 of a comparative example.
- the CNT device 17 could be manufactured by peeling the copper thin film 18 from the Si substrate (heat-resistant uneven substrate 6) (see the successful example on the left side of FIG. 19).
- the copper thin film 18 is a thin film having a thickness of about 10 ⁇ m, the copper thin film 18 is easily broken and difficult to handle. Therefore, when the copper thin film 18 is torn when peeling the copper thin film 18 from the heat-resistant uneven substrate 6 (see the upper left and lower left drawings of the failure example in FIG. 19), the copper thin film 18 is broken and the heat-resistant uneven substrate 6 is removed. There was a case where it could not be peeled off (see the upper right figure of the failure example in FIG. 19).
- the CNT devices 19a and 19b of the reference example have a CNT layer 2'formed on a smooth heat-resistant substrate 6 '.
- Fe 4 nm / Al 15 nm was carried on the Si substrate surface using RF magnetron sputtering (STEP 2).
- the thickness of the CNT layer 2 ′ was 10 ⁇ m.
- the thickness of the CNT layer 2 ′ was 63 ⁇ m.
- brazing material layer 3 (Ag-Cu brazing material layer) on the surface of the CNT layer 2 '(STEP 4).
- the film thickness of the brazing material layer 3 of the CNT devices 19a and 19b was 3.5 ⁇ m and 3.3 ⁇ m, respectively.
- the metal pedestal 4 was provided on the brazing material layer 3, and the metal pedestal 4 was brazed to the CNT layer 2 ′ by heating for 1 minute under the conditions of 800 ° C. and Ar 10 Torr (STEP 5). After brazing, the metal pedestal 4 was peeled off from the Si substrate to manufacture the CNT devices 19a and 19b of the reference example (STEP 6).
- the CNT layer 2 ′ was transferred to the metal pedestal 4. However, it was difficult to transfer the uniform CNT layer 2 ′ onto the surface of the metal pedestal 4. It is considered that this is because on the smooth heat-resistant substrate 6 ′, the surface of the CNT layer 2 ′ also becomes a smooth surface, and the brazing material layer 3 vapor-deposited thereon is easily peeled off. Further, the surface of the CNT layer 2 ′ after being transferred to the metal pedestal 4 had a flat surface as compared with the CNT layer 2 of the example.
- the surface of the CNT layer 2 ′ formed on the heat resistant substrate 6 ′ had a flat surface as compared with the CNT layer 2 of the example. Further, cracks were observed in the brazing material layer 3 formed on the CNT layer 2 '. It is considered that this is because the surface of the CNT layer 2'is smooth, so that the brazing material layer 3 is easily separated from the CNT layer 2 '.
- the FE performance of the CNT devices 19a and 19b of the reference example was one to two digits lower than that of the CNT devices of the examples.
- the first brazing filler metal layer 31 is formed on the CNT layer 2 after going through the same STEP1 to STEP3 as in FIG. 2 (STEP4a). Then, the second brazing material layer 32 is formed on the first brazing material layer 31 (STEP 4b). As a result, the brazing material layer 3 having a multi-layered structure including the first brazing material layer 31 formed on the CNT layer 2 side and the second brazing material layer 32 formed on the metal pedestal 4 side is formed. The Rukoto.
- Each of the first and second brazing material layers 31 and 32 can be formed by appropriately applying a method similar to that of the brazing material layer 3 in FIG.
- the brazing materials having different melting points may be applied.
- a brazing material having a relatively high melting point (Cu in Example 8 described later) is applied to the first brazing material layer 31 close to the CNT layer 2, and the second brazing material layer separated from the CNT layer 2 is used.
- a brazing material having a relatively low melting point (Ag—Cu alloy in Example 8 described later) may be applied.
- the metal pedestal 4 is brazed to the CNT layer 2 (STEP 5a).
- Brazing is performed by heating to a temperature at which the brazing material of the second brazing material layer 32 melts.
- the melting point of the Ag-Cu alloy is 779 ° C, so it is preferable to heat the material to 779 ° C or higher for brazing, and to use another brazing material.
- the brazing temperature is adjusted according to the melting point of the brazing material.
- the heat-resistant concavo-convex substrate 6 is peeled from the CNT layer 2 to form the CNT device 1 '(STEP 6a).
- the first and second brazing material layers 31 and 32 may be provided on the metal pedestal 4 side. In this case, first, the second brazing material layer 32 is formed on the metal pedestal 4, and then the first brazing material layer 31 is formed on the second brazing material layer 32.
- Example 8 below relates to a CNT device manufactured based on the manufacturing method shown in FIG. 23, and shows observation results, evaluation results, etc. of the CNT device.
- Example 8 In the CNT device 20 of Example 8, as in Example 7, a plurality of metal pedestals 4 are arranged on the brazing material layer 3 (the second brazing material layer 32 in Example 8) on the CNT layer 2 to form a metal pedestal. 4 to which the CNT layer 2 is brazed.
- CNTs were synthesized on a Si substrate by the same method as in STEP 1 to STEP 3 of Example 1.
- CNT was synthesized at 700 ° C. for 1 minute.
- first brazing material layer 31 Cu brazing material layer
- first brazing material layer 31 Cu brazing material layer
- Ag—Cu alloy silver braze; BAg-8
- a brazing material layer 32 Ag—Cu brazing material layer was formed (STEP 4b).
- the brazing filler metal layer 3 having a two-layer structure (that is, the Cu brazing filler metal layer and the Ag—Cu brazing filler metal layer) is formed on the surface of the CNT layer 2.
- the deposition time of each of the first and second brazing filler metal layers 31 and 32 of the CNT device 20 was 10 seconds, and the thickness thereof was 0.5 ⁇ m (the total thickness of the brazing filler metal layer 3 was 1.0 ⁇ m). It was
- a plurality of metal pedestals 4 were provided on the brazing material layer 3 (the second brazing material layer 32 in Example 8), and the CNT was heated for 1 minute under the conditions of 800 ° C. and Ar 10 Torr.
- the metal pedestal 4 was brazed to the layer 2 (STEP 5a). After brazing, the metal pedestal 4 was peeled off from the Si substrate (heat-resistant concavo-convex substrate 6) to manufacture the CNT device 20 of Example 8 (STEP 6a).
- the brazing material layer 3 is automatically cut into the shape of the metal pedestal 4, and the CNT layer 2 is transferred by the metal pedestal 4 in accordance with the shape of the metal pedestal 4, as shown in FIG. It was Further, the shape of the brazing material layer 3 on the heat-resistant concavo-convex substrate 6 side was not substantially disturbed, and the CNT layer 2 was transferred onto the entire surface of the metal pedestal 4 without protruding uniformly. No exudation of the brazing material was confirmed on the surface of the CNT layer 2.
- the reason why the exudation of the brazing filler metal does not occur is that the first brazing filler metal layer 31 of the brazing filler metal layer 3 has a relatively high melting point, so that the first brazing filler metal layer 31 functions as a barrier layer. It was found that the brazing material functions and the excessive penetration of the brazing material into the CNT layer 2 is suppressed.
- the handling of the CNT device 1 becomes easy. That is, by directly providing the brazing filler metal layer 3 on the CNT layer 2, the CNT formed in a thin film shape can be bonded to an arbitrary component by heat treatment.
- a mixed layer 5 in which the brazing material is soaked in the CNT is formed between the CNT layer 2 and the brazing material layer 3.
- the electric resistance between the CNT layer 2 and the brazing material layer 3 is reduced, and the adhesiveness between the CNT layer 2 and the brazing material layer 3 is improved.
- the brazing material layer 3 and the metal pedestal 4 are brazed, the brazing material layer 3 is melted and the unevenness of the surface of the brazing material layer 3 in contact with the metal pedestal 4 is absorbed.
- the electric resistance between the brazing material layer 3 and the metal pedestal 4 becomes low, and the joint becomes strong.
- the conductivity and adhesiveness between the CNT layer 2 and the metal pedestal 4 are improved. Therefore, when the CNT device 1 is applied to the emitter, scattering of the emitter due to a high electric field is suppressed.
- gas release from the brazing material layer 3 is suppressed even when the CNT device 1 is provided in a vacuum.
- a first brazing material layer 31 formed on the CNT layer 2 side and a second brazing material layer 32 formed on the metal pedestal 4 side and having a lower melting point than the first brazing material layer 31 In the case of the multi-layered structure having, the excessive penetration of the brazing material into the CNT layer 2 is suppressed.
- the CNT layer 2 on the heat-resistant concavo-convex substrate 6, the concavity and convexity on the surface of the CNT layer 2 of the CNT device 1 can be easily controlled. As a result, the CNT device 1 having excellent emitter performance can be manufactured. Further, by forming the CNT layer 2 on the heat-resistant uneven substrate 6, the unevenness is formed on the surface of the CNT layer 2 on the heat-resistant uneven substrate 6. By providing the brazing material layer 3 on the uneven surface, the bonding between the CNT layer 2 and the brazing material layer 3 is strengthened, and the transfer of the CNT layer 2 to the metal pedestal 4 becomes good.
- the metal pedestal 4 fixing the metal pedestal 4 to the CNT layer 2 before peeling the heat-resistant concavo-convex substrate 6 from the CNT layer 2, deformation of the CNT layer 2 can be prevented, and handling at the time of incorporating the CNT device 1 into an apparatus. Will be easier. More specifically, when incorporating the emitter into the X-ray tube, the emitter can be easily incorporated into the X-ray tube by mounting the metal pedestal 4 inside the apparatus. In the case where the copper thin film 18 is directly provided on the CNT layer 2 (see FIG. 19) as in the conventional case, the thickness of the finished device (thickness of the copper thin film 18) is about 10 ⁇ m, which is suitable for X-ray tubes.
- the CNT device 1 When mounted as an emitter, it was necessary to sandwich and fix the end of the thin film with other components. As a result, an increase in the size of the fixed part is unavoidable, which is a factor that hinders the size reduction of the X-ray tube.
- the CNT device 1 according to the embodiment of the present invention facilitates the handling (therefore, the fixing portion of the CNT device 1 is simplified), thereby reducing the size of an apparatus such as an X-ray tube. realizable.
- the plurality of metal pedestals 4 on the CNT layer 2 formed on the heat-resistant concavo-convex substrate 6 with the brazing material layer 3 interposed therebetween it is possible to easily manufacture the plurality of CNT devices 1.
- the manufacturing cost of the device 1 can be significantly reduced (see, for example, FIG. 17).
- the CNT device 1 since unevenness corresponding to the surface unevenness of the heat-resistant uneven substrate 6 can be formed on the surface of the CNT layer 2, the surface uneven shape of the CNT layer 2 can be easily controlled. be able to. Further, by using the heat-resistant concavo-convex substrate 6 as a reusable template substrate, the manufacturing cost of the CNT device 1 can be reduced.
- the CNT layer 2 By forming the CNT layer 2 by CVD, the CNT layer 2 including the CNT aggregate and the CNT aggregate vertically aligned with respect to the heat-resistant concavo-convex substrate 6 (that is, the surface of the CNT layer 2) is formed. You can
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Abstract
Description
次に、図2に基づいて、本発明の実施形態に係るCNTデバイス1の製造方法の一例について、詳細に説明する。
本発明の実施例1として、本発明の実施形態に係るCNTデバイスの製造方法(図2)より、X線装置のエミッタに適用可能なCNTデバイス1a、1bを製造した。この実施例では、耐熱凹凸基板6としてSi基板、金属台座4としてφ6mm厚さ4.5mmの銅台座、ろう材としてAg-Cu合金を用いた。また、触媒7はFeを用い、担体層8はAlOxを用いた。
実施例2では、Ag-Cuろう材層の厚さが26.7μmのCNTデバイス11を作製した。この実施例では、耐熱凹凸基板6としてSi基板、金属台座4としてφ6mm厚さ4.5mmの銅台座を用いた。なお、実施例2の説明において、実施例1と同様の工程(STEP1~STEP3の工程)については、詳細な説明を省略する(実施例3~7も同様である)。
実施例3では、Agろう材層の厚さが35.3μmのCNTデバイス12を作製した。この実施例では、ろう材の種類が異なることを除いて、実施例2と同様の方法でCNTデバイス12を作製した。
実施例4では、ろう付け時間の異なる3つのCNTデバイス13a~13cを作製した。この実施例では、ろう材層の厚さとろう付け温度とろう付け時間が異なることを除いて、実施例1と同様の方法でCNTデバイス13a~13cを作製した。
実施例5では、Ag-Cuろう材層の厚さの異なる3つのCNTデバイス14a~14cを作製した。
実施例6では、ろう付け温度とろう付け時間の異なる2つのCNTデバイス15a、15bを作製した。
実施例7のCNTデバイス16a、16bは、図17に示すように、CNT層2上のろう材層3に複数の金属台座4を配置して、金属台座4にCNT層2をろう付けしたものである。
比較例のCNTデバイス17は、CNT層2の表面に直接集電体(銅薄膜18)を設けたものである。
参考例のCNTデバイス19a、19bは、平滑な耐熱基板6'上にCNT層2'を形成したものである。
次に、図23に基づいて、本発明の実施形態に係るCNTデバイス1の製造方法の他例について、詳細に説明する。なお、図2と同様のものには、同一符号を引用する等により詳細な説明を適宜省略し、主に図2との差異点を中心に説明する。
実施例8のCNTデバイス20は、実施例7と同様に、CNT層2上のろう材層3(実施例8では第2ろう材層32)に複数の金属台座4を配置して、金属台座4にCNT層2をろう付けしたものである。
Claims (16)
- 繊維状炭素を含む炭素膜層と、
前記炭素膜層に直接備えられるろう材層と、
前記ろう材層を介して前記炭素膜層に備えられる金属台座と、を備える炭素-金属構造体。 - 前記炭素膜層は、表面に平均高さ1μm~100μmで高さ/間隔比が1/5~5/1の凹凸を備える、請求項1に記載の炭素-金属構造体。
- 前記炭素膜層は、予め基板上に形成された層であり、
前記ろう材層は、前記炭素膜層の前記基板と接した面と反対側の端部に形成された層である、請求項1または請求項2に記載の炭素-金属構造体。 - 前記ろう材層は、金属ろう材により形成される層であり、
前記炭素膜層と前記ろう材層との界面には、前記炭素膜層に前記ろう材層を形成するろう材がしみ込んだ混合層が形成された、請求項1から請求項3のいずれか1項に記載の炭素-金属構造体。 - 前記ろう材層は、炭素膜層側に形成されている第1ろう材層と、金属台座側に形成され当該第1ろう材層よりも低融点の第2ろう材層と、を有した多層構造である、請求項1から請求項4の何れか1項に記載の炭素-金属構造体。
- 前記ろう材層の厚さは、1μm以上であり、50μm以下である請求項1から請求項5のいずれか1項に記載の炭素-金属構造体。
- 請求項1から請求項6のいずれか1項に記載の炭素-金属構造体を備える、電子エミッタ。
- 請求項7に記載の電子エミッタを備える、X線管。
- 基板に繊維状炭素を含む炭素膜層を形成する工程と、
前記基板に形成された炭素膜層にろう材層を形成する工程と、
前記炭素膜層に、前記ろう材層を介して金属台座をろう付けする工程と、
前記炭素膜層から前記基板を取り除く工程と、を有する炭素-金属構造体の製造方法。 - 前記ろう材層は、前記炭素膜層に蒸着された金属ろう材を含む、請求項9に記載の炭素-金属構造体の製造方法。
- 基板に繊維状炭素を含む炭素膜層を形成する工程と、
前記基板に形成された炭素膜層を支持する金属台座にろう材層を形成する工程と、
前記炭素膜層に、前記ろう材層を介して金属台座をろう付けする工程と、
前記炭素膜層から前記基板を取り除く工程と、を有する炭素-金属構造体の製造方法。 - 前記ろう材層は、炭素膜層側に形成される第1ろう材層と、金属台座側に形成され当該第1ろう材層よりも低融点の第2ろう材層と、を有する多層構造である、請求項9から請求項11の何れか1項に記載の炭素-金属構造体の製造方法。
- 前記炭素膜層を、化学気相成長法により前記基板に形成する、請求項9から請求項12のいずれか1項に記載の炭素-金属構造体の製造方法。
- 前記基板は、表面に平均高さ1μm~100μmで高さ/間隔比が1/5~5/1の凹凸を備える、請求項9から請求項13のいずれか1項に記載の炭素-金属構造体の製造方法。
- 前記炭素膜層から取り除かれた基板を、他の炭素-金属構造体の炭素膜層を形成する基板として再利用する、請求項9から請求項14のいずれか1項に記載の炭素-金属構造体の製造方法。
- 前記炭素膜層に、前記ろう材層を介して複数の金属台座をろう付けする、請求項9から請求項15のいずれか1項に記載の炭素-金属構造体の製造方法。
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