TW200815282A - Carbon nanomaterial, manufacturing method therefor, electronic element and electronic device - Google Patents

Abstract

The present invention provides a carbon nanomaterial which is formed by at least one of the carbon nanotube material and graphene material, and is manufactured by the following method: irradiate vacuum ultra violet rays (VUV) onto the carbon nanotube material; provide the material for surface modification of the carbon nanotube material by providing the combination with the VUV. Thus, a novel carbon nanotube material with increased affinity to bond with the other materials can be obtained by the present invention.

Description

200815282 IX. Description of invention:

The invention relates to a surface modification technique for a carbon-based nanomaterial. The invention relates to a surface modification technique for a carbon-based nanomaterial. In the semiconductor integrated circuit device including a semiconductor device and a printed wiring board, in the electronic component having the properties of a conductor and a heat conductor, the so-called carbon nanoeed is used. Rice tube (CNT) technology. 10 In particular, 'CNTs have excellent chemical stability, excellent physical properties, electrical properties, and other characteristics, and are attracted by the formation of semiconductor devices, such as the control of their thickness and length. The control and the control of the spatial spiral characteristics, etc., have been carried out in various studies. In the specific application, the electromagnetic wave shielding member for electronic equipment, the cooling bump material for high-performance electronic components such as super LSI, and the wiring via structure of the semiconductor device and the components of the semiconductor device (such as electricity) Gate electrode of the crystal, source electrode, drain electrode, channel electrode, etc.). The following applications can be considered, for example, using CNTs having extremely high thermal conductivity of CNTs, the CNTs are grown on a semiconductor process substrate at a high density, and are used as a part of the conductive circuit or mounted on the process substrate. The heat transfer path of the upper electronic component (semiconductor device) and the heat dissipation path for dissipating heat generated by the heat generated by the structure (the so-called "bump structure") may be considered as follows. In one application, the high electrical conductivity is used as a through-hole wiring structure in a high-density wiring structure of a semiconductor device (semiconductor element) having an ultrafine structure. An example in which the CNT is used as a cooling bump material for a high-performance electron element (for example, see Non-Patent Document 1). As shown in Fig. 5, the cold of such a high-performance electronic component is used. " However, the bump structure can be manufactured by, for example, a coating on a substrate (aluminum nitride (AIN, aluminum, etc.)) 51 on the substrate 52 by a enamel plating or the like. Is a mounting film (such as a TiN film) and a catalytic metal film (c〇, etc.) (both 10 are combined by reference numeral 53)' followed by thermal CVD using a hydrocarbon-based gas (cjj4, 63⁄4, etc.) After the CNT 54 is grown, the conductive material (such as a metal such as C11 or A1) is adhered to the CNT portion of the CNT substrate by plating (wet treatment) or the like. In order to fabricate a €1^ bump structure, the electronic component can be heat-pressed (preferably 25 Å. (: 15 deg. 15 degrees) on the substrate to produce a highly thermally conductive electronic component. In the first aspect, an example of a wiring via structure using the CNT (see, for example, Patent Document 1 and Non-Patent Document 2) is shown in Fig. 1. As shown in Fig. 1, the through-hole structure can be manufactured by the following procedure. That is, a base layer 2 and a Cu wiring layer 3' are provided on the base, and a barrier film (Ta film) 4 for preventing the diffusion of Cu is deposited on the Cu wiring layer 3, and insulation is provided on the barrier film 4. After the film 5' is further provided with a through hole, a catalyst metal mounting film (such as a Ti film) 6 and a catalyst gold such as Co are deposited by sputtering or the like. The film (or the catalyst fine particle layer) 7 is formed by heating the CNT 8 by a thermal cVD method (thermal chemical vapor deposition method) using a hydrocarbon-based gas (CH4, QH2, etc.) or the like, and then forming an upper wiring. Fig. 6 200815282 also exemplifies a filling of the intestines 9 for fixing the CNTs 8. Patent Document i: Japanese Patent Laid-Open Publication No. _32 (No. of the patent application) Patent Document 2 (Required Patent 5) Non-Patent Document 1: Fujitsu Co., Ltd., Fujitsu Research Co., Ltd., "World Premiere! Use of Nanotubes for Semiconductor Wafers/Hybrid Substrates" (above) The original Japanese text is ·· f Shitong Co., Ltd., Fujitsu Research Institute, "The beginning of the world! Force one seeks ^10^Twenty-one y 1 〇蚤 half $ 千7 7 0 exothermic substrate 匕"", December 5, 2005, [August 18, 2006 search] 'Internet, <皿[:卿年利敝嶋如/崎8/2〇〇5/12/5^咖非非文文2 · 一瓿专卖者,r japanese journai 0f Applied Physics》 (The above Japanese text is two bottles & 16:21, 15, 1 and 10; 1/·彳·7. Today, 4th and 47th, only"), _ 2005, 44th, pl626. t ^^明内] Summary of the Invention However, although the carbon nanotube itself has excellent conductivity, semiconductor, bismuth, thermal conductivity, chemical stability, etc., the following problems are known, namely, with other materials. When the bonding property is insufficient, the electrical conductivity and thermal conductivity of the continuous smear may be greatly lowered, and problems such as interlayer adhesion and adhesion may not be obtained. Further, this problem occurs in the case where one end of the substrate is fixed and the nanotubes obtained by CVD are used for wiring 7 200815282. This problem can be solved by completely adhering the part to the peripheral layer of the cnt when manufacturing the part. However, in the case where the incompatibility of the interface between the CNT and other materials cannot be solved, there is a problem that the above-mentioned 5 closeness cannot be achieved. This is also a common problem for CNTs in all uses. In general, CNTs are produced by conventional methods (Laser Burner, :_), Chemical Vapor Deposition (CVD), HiPC (High-Voltage Carbon Monoxide • Pyrolysis (High_P Lai Carbon)) And so on. The surface molecular structure of the CNTs of the CNTs, which are obtained by the aforementioned method, is related to the nature of the electronic super-common structure of the benzene ring, and the frost between the other materials. Wetness also shows the quality of graphite, such as graphite. That is, the surface of the molecule that has been produced (4) in its original state (such as powder), regardless of the view of the _, the good material of the ship, even if it is treated under conditions (such as when supersonic processing with ethanol), most However, it is a limit that can be obtained by obtaining a degree of dispersion for several weeks. This is a great limitation of CNTs in various engineering applications. In other words, when the CNT and the other material are mixed with each other, for example, when the CNT and the resin are functionally mixed with the structural material production line, the operation is performed in the vertical direction or by kneading with other materials, '2G. In the case of no additives such as surfactants, it is not easy to produce ultra-fine composite materials with excellent phase I4, and when the force is added to the mouth, it is difficult to escape the properties of the material. Adverse effects (such as the decline in electrical properties = mechanical strength, chemical degradation, etc.). Here, the decrease in electrical properties is such as an increase in electrical resistivity and a reliable maintenance of electrical properties in the medium and long term. 8 200815282 degree reduction, increase in resistivity per weight, deterioration in electromagnetic shielding performance, and reduction in equivalent sin. Further, the decrease in mechanical strength means a decrease in rigidity rate, a breaking strength, and a deterioration in long-term performance of the above two. Further, a decrease in chemical properties indicates deterioration of material properties (e.g., hygroscopicity, solvent resistance, oxidation due to oxygen in the air) which are resistant to the environment. For example, the CNT can be used as a material for via wiring of a high-density, high-machine-made electronic device such as a super LSI, and it is necessary to cut and grow it by Cmp (Chemical Mechanical Polishing). The upper end of the CNT in the hole. At this time, in order to fix the CMT bundle, or to perform CMP, the abrasive material and the polishing liquid flow into the CNT bundle to contaminate the inside of the CNT (or can be easily removed after the inflow), and the insulating material is required. When the CNT bundle is fixed by other substances, if the affinity of the CNT to the insulating material or the like is not good, the resin which has been dissolved in the /sol can be applied by spin coating or the like. The method, or the method of manufacturing a resin 1S-like substance in a vacuum environment, is still unable to sufficiently fill the insulating material between the CNT bundles, so that there is a slight volume of space around the CNT bundle. And it is impossible to allow other substances to smoothly mix into the CNT bundle. In view of the above problems, several countermeasures have been proposed (see Patent Document 2), but they are not sufficient. 2. In addition, the above is only for the description of the carbon nanotubes, but the characteristics and limits of the carbon nanotubes as described above are also applicable when applied to electronic component parts using graphite sheets, and the aforementioned graphite; A structure obtained by cutting a cylinder of a carbon nanotube in the longitudinal direction. That is, the surface of the graphite sheet is not easily wetted by other substances, and when the electronic component is produced by this property, if it is desired to form a shape, the possibility of forming a void directly in this state is increased. The present invention aims to provide a carbon nanotube-based material which can improve the affinity when the CNT is bonded to other materials, and a carbon-based nanomaterial including a graphite sheet-based material. Further objects and advantages will be apparent from the following description.

According to one aspect of the present invention, a surface-modified carbon-based nanomaterial is provided, and the surface thereof is modified and composed of at least a carbon-based nano tube material and a graphite y-based material. The method for producing a carbon-based nanomaterial, wherein the carbon-based nanomaterial composed of a carbon-based nanotube material and a graphite sheet-based material comprises the following program, that is, : irradiating a vacuum ultraviolet ray; and providing a substance capable of modifying the surface of the aforementioned nanomaterial by a combination with the vacuum ultraviolet ray. ▲ According to the aspect of the invention, it is possible to obtain a novel carbon-based nanomaterial which is affinity-friendly when it is joined to other materials. According to another aspect of the present invention, there is provided a surface-modified carboniferous carbonaceous carbon which is composed of carbon composed of at least (10), a nanomaterial, and an ink sheet material. A nanomaterial is prepared by the method of the following procedure, namely: irradiating a vacuum ultraviolet ray; and providing a substance capable of modifying the surface of the material by a combination of non-true lines. 10 200815282 2 The anti-twist nanomaterial that is bonded to the (four) material can be suitably used for all f sub-components of electronic novels and the like. 〜转等, 电子零五质=!! The above-mentioned "the same kind, the material of the carbon-based nanomaterial can be the chemical that can be changed by the surface of the vacuum line plus = For active species, the above-mentioned reference surface: 14 atomization and atomic nano-materials should be prepared by CVD method: carbon-based modified nano-materials which can be modified and modified are suitable for growth. On the substrate, the surface of the substrate is composed of a conductive material, an insulating material f, a hydrophilic substance, a substance consisting of a substance having a specific group, and the surface of the surface is modified before the surface is modified. The chemical affinity species such as the chemically active species such as the atomic group of the 15 f electron-donating group of the rice material, and the chemically active species such as the original publication of the 7-substance group, etc. At least ^ and electricity can be used to modify the surface of the carbon-based nanomaterials, it should be included in the right:, by oxygen, amines, halogens, alcohols, ethers and two selected from the group At least one substance, again, can be;; the material of the surface modification of the two parts is the surface quality:,:= , 20 :; r described vacuum purple ~ Naida according to other aspects of the invention, can provide electronic components including the aforementioned surface modification materials (four) into, in particular, provide through holes, heat dissipation II, ::; or conductivity Sheet, electromagnetic wave shielding material sheet, used to make: special sheet material, (10) including surface silk surface modified carbon system;; 11 200815282 material composed of electronic devices. According to the above two aspects of the present invention, an electronic device, an electronic component, and the like which utilize the superior characteristics of the carbon-based nanomaterial can be realized. Effect of invention 5

10 15

According to the present invention, a novel carbon-based nanomaterial which has an improved affinity when joined to other materials can be obtained. This material can be applied to electronic equipment and electric parts. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a through-hole structure of a CNT. Fig. 2 is a schematic view showing a main portion of a device for irradiating a vuv of the present invention and supplying a specific object handle. Fig. 3 is a schematic view showing the main part of a device for illuminating the vuv of the present invention and supplying a specific object handle. 1 is a cross-sectional view schematically showing a semiconductor integrated circuit device in which a carbon-based nanotube structure of the present invention is applied to a via hole.珥#- Fig. 5 is a schematic view showing a schematic example of an electronic component including a high thermal conductivity bump which is used for cooling a bump of a high-hard electronic component. Material ±. , shoulder Fig. 6 is a schematic view showing an outline of the manufacturing method when the present invention is applied to an electromagnetic wave shielding material. 'Water' Figure 7 is a schematic cross-sectional view of an untreated graphite sheet. Figure 8 is a schematic representation of a processed graphite sheet of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 12 200815282 5 10 15 20 The following is a description of the embodiments of the present invention. However, the technical scope of the present invention is not limited to the embodiments described below, and can be extended to the scales and scales contained in the patent application. Further, as described above, the present invention is a graphite sheet material which is made of the same type of moisture and has the same problem of moisture resistance. Therefore, the carbon nanotube-based material: the graphite sheet-based material is referred to as a "carbon-based nanomaterial". The surface modified carbon nanomaterial of the present invention can be obtained by including the following spear. By the method of sequencing, that is, the carbon-based nano material is irradiated with a vacuum ultraviolet (VUV · Vacmim Ultra vi〇let rays), and by the combination of the carbon-based nano material ^νυν, the carbon can be provided A material modified by the surface of a nanomaterial (hereinafter, a substance that can modify the surface of a carbon-based nanomaterial by the combination of the carbonaceous nanomaterial and νυν) is called a "specific substance". ). ,

The reason why the surface of the carbon-based nanomaterial can be modified by irradiating the carbon-based nanomaterial with VUV and supplying the precursor, and L is that the substance can be activated by the weight to generate the original; Group = active species, and the chemical species will act on the surface of carbon-based nanomaterials. The mechanism can be presumed to be as follows (2) and the nature of the right and wrong of women is irrelevant). That is, the vuv irradiation is received, and the bond is broken in a specific substance suspended in the vicinity of the W and the U tube, and the wood tube is in the vicinity of the W piece, = oxygen, amine radical, sulfonium atom, c 2 chemistry Sexual species. Because the aforementioned atomic group is not stable: Sub: 匕 will quickly 舆 near the nanotubes and graphite sheet on the reactivity: due to the part of the five-door defect reading, usually called the dangling bond unstable (four) / 疋 graphite The chemically active moiety on the end of the sheet is bonded to form a conjugate 13 200815282. Alternatively, it is not directly chemically bonded to the nanotube and the graphite sheet, but is reacted with a chemical active species such as an atomic group and bonded again. A higher (low volatility) product of peach formation, the domain product is adsorbed on the surface of the meter tube molecule and the graphite sheet. 5 In addition to the above, there may be other mechanisms, such as the substance or part-adsorption On the surface of carbon-based nanomaterials, and by using it, without the use of atomic rings, etc., the formation of the tongue-like species acts on the surface of the carbon-based nanomaterial. The above-mentioned 3 7 + 乍 uses this 疋 to use chemical bonding as the main body, but there may be physical absorption and observation, and the above-mentioned mechanism and mode of action are not related to the essence of the present invention. Specific substances in the narrative, The surface of the nanomaterial can be modified by the meaning of =. Moreover, when the specific substance is in contact with the carbon-based nano-material, when the surface of the 15 = meter material is also modified, it is known that the surface modification is specific. 』 'This kind of surface modification can be changed by the change of surface tension, the hygroscopicity of the specific solvent, the change of the amount of adsorption of the mosquito-based (such as polar group) into the broken substance, etc. The change in the adhesion between the materials, the specific surface modification, or the modification is confirmed by the formula of the carbon-based nanomaterial in a certain sense. Such a modification t is improved by using vuv. As a result, the affinity with other substances, as described above, may be due to the fact that a substance of a chemically active species such as an atomic group which can be generated by a vuv is a multi-phased or a specific substance, and may not comply with the above-mentioned 14 200815282. a change, and a substance which can generate a chemically active species such as an atomic ring by νυν is considered as a specific substance. The reason is that if a chemically active species such as an atomic group is generated, theoretically, the surface of the carbon "m" There are some variations in the production. 5 Chemically active species such as such an atomic group, preferably containing a chemically active species such as an electron-donating group such as an atomic group thereof, and at least an electron-active group such as an atom-group thereof When a chemically active species such as an atomic group is involved, a polar group is introduced into a carbon-based nanomaterial, and affinity with a substance having polarity can be improved. Further, in the present invention, "surface "refers to the surface in the so-called surface modification, not only the outermost surface of the stone inverse nanomaterial, but also the surface and inner surface of the depression, but, in connection with the present invention, specifically, the carbon-based nanomaterial It is not important where the modification is carried out. The specific substance in the present invention is not particularly limited and may be taken from any of the materials. Specifically, it is preferable to choose which type of surface modification to perform. For example, when the affinity for a polar solvent is increased, it is preferably a substance which can introduce a polar group to the surface of the stone reaction material. When the solubility of the solvent 2 having a specific structure is improved, it is a chemical structure which can be defined by (4), or a material which is adjacent to the structure and which is introduced into the surface of the carbon-based nanomaterial. It is also possible to adjust the degree of hydrophilicity and lipophilicity of the stone-reversing nano-material by adjusting the type of the group of the raw group and the lipophilic group and the amount of introduction. At least one of a group consisting of oxygen, an amine, a halogenated type, a class, a scale, and a mixture of the foregoing, "said, using the foregoing substance, the carbon-based nanomaterial can be improved. Table 15 200815282 The talent of the face is born. The supply of the ruthenium material is carried out in the vapor phase in order to allow the specific substance to collide with the carbon-based nanomaterial. When the steam is supplied to the specific 5 = at room temperature and at room temperature, since there is also a h shape in which the vapor pressure is low or it is difficult to evaporate I, it is preferable to use a decompression method as described later or by / The NJ* biological shell is diluted with the inert substance method, the specific substance method is heated, and the like. The preparation of the cockroach material itself does not necessarily have to be steam. Therefore, it is also possible to hunt by the mist of the mouth and suspend it in other gases in the state of the mouth, and the specific substance that may be suspended in the mouth/this day is directly used to contribute to the stone-reversing nanomaterial. Upgraded. The nature and extent of the modification of carbon-based nanomaterials are influenced by the type of specific substance supplied. For example, when the surface of the carbon-based nanomaterial is introduced into the surface of the carbon-based nanomaterial, the affinity for an alcohol-based solvent such as ethanol or ethylene glycol (diol) glycerol 15 (triol) can be improved. . Further, when an amine group is introduced or an amine group or an amine group-containing compound is adsorbed, the affinity for the solvent having an amine group functional group such as dimethylamine (DME) or the like can be improved. According to the experiment, the nanotubes on the Si substrate filled with triethylamine or a mixture of ammonia and hydrazine were introduced into the amine group 20 by VUV irradiation. Similarly, when a thiol (-SH) group or a plurality of functional groups containing the thiol group or a compound is introduced or adsorbed, the affinity for each solvent is improved. Further, when an amine group and a hydroxyl group are simultaneously introduced, for example, affinity with TMAH (tetramethylammonamine hydroxido (an imaging agent such as tetramethylammonamine hydroxido) is greatly improved). The ultraviolet rays can be classified into UV-A having a wavelength exceeding 315 nm and in a range of 400 nm or less, υν-β having a wavelength exceeding 280 nm and in a range of 315 nm or less, UV-C having a wavelength exceeding 200 nm and in a range of 280 nm or less, and a wavelength such as (5) 5 Νυν in the range of 200 nm, the carbon-based nanomaterial of the present invention has high stability (chemical stability, etc.) with respect to a general surface, and cannot be sufficiently surface-modified or modified by UV irradiation of Uv_A to uv_c. At a speed of k, it can be found that when VUV is combined with the above-mentioned specific substances, the means for obtaining the aforementioned effect of 0 10 (four) sense vuv is not produced (4). It is recommended that the bribe should be a narrow and wide-width 6-molecular ^^^ lamp with a central wavelength of 17211111. In general, it is preferable to display a wavelength distribution of about 160 nm to 200 nm, that is, a quasi-molecular UV lamp of <Xe, but it is not limited to this example. χ, the bond dissociation energy of the organic compound is directly related to the wavelength of the VUV, so that the specific wavelength dissociation 15 is excluded. The VUV wavelength range can also be limited to a narrow range depending on the purpose. There is no limit to the output of νυν, and you can use the tens of mW/cm private exporters sold in the market. In addition, as long as there is no problem in the cooling and arrangement of the devices (excimer VUV lamps, etc.) that can be generated, the output of the output is increased, or the VUV lamps are placed close to each other and the majority is _, increasing the actual side of each side. The amount of exposure may also be related to increased productivity. Further, νυν is used as a name, and is generally used in a vacuum or under reduced pressure. However, the present invention is not limited thereto and can be used under normal pressure. The VUV exposure in the 毛本毛月 is carried out on carbonaceous materials in a decompressed or atmospheric environment 17 200815282 5 • 10 nanometer material. By controlling the combination of VUV and specific substances, and expanding the distance between VUV and carbon-based nanomaterials, this practical significance is to control the concentration of specific substances in the environment surrounding carbon-based nanomaterials. The system can work. This is because, for example, in air containing 20% by volume of oxygen, in order to allow VUV to absorb almost all within 1 cm, the specific substance is mostly a large extinction coefficient, so most of the time it is preferable to reduce the concentration of a specific substance by some means ( Or vapor pressure, partial pressure, etc.). Although the above operation can be carried out by adjusting the degree of decompression of the environment, a specific substance which is diluted with a vertical or irradiated VUV and which does not modify the surface of the carbon-based nanomaterial, that is, an inert substance, is also used. There are many more ideal occasions. Specifically, in a normal pressure state, it is preferred to dilute a specific substance between 0.001 and 50% by volume, more preferably between 0.01 and 10% by volume. Further, the inert substance is not particularly limited, and since the environment of the present invention is a gas phase, in general, 15 gas substances or volatile substances are suitable. An inert gas such as helium, argon or the like and nitrogen may be exemplified as preferred. Regarding the object to be irradiated, that is, the distance between the carbon-based nanomaterial and the νυν irradiation source is preferable because it is easily absorbed by νυν. Although there are some differences between the type of the carbon-based nanomaterial and the νυν source, and the concentration (or vapor pressure or atmospheric pressure), in general, the distance is preferably from 0.1 nm to 100 nm. In other words, more often it is 0.2 nm to several cm. The manner of VUV irradiation is not particularly limited. The supply of specific substances may not be carried out simultaneously. The method of continuously supplying the specific substance 18 200815282 to the carbon-based nanomaterial and continuously performing νυν irradiation, or intermittently supplying the specific substance to the carbon-based nanomaterial, may be exemplified. The supply time is intermittently performed by νυν irradiation, or the specific substance is intermittently supplied to the carbon-based nanomaterial, and the supply time is matched, and the supply is intermittently performed at a later time, and the νυν is intermittently irradiated. The method. It is not known whether the surface modification of carbon-based nanomaterials will only occur when directly irradiated to νυν. For example, when the chemically active species such as the generated atomic group have a long life, it is presumed that surface modification is not caused by direct irradiation to the VUV. Therefore, the entire carboniferous nanomaterial is irradiated with νυν, and as a result of 10, if the surface is modified, it is in accordance with the gist of the present invention. In general, it is preferable to directly irradiate each of the carbon-based nanomaterials to VUV. Therefore, it is preferable that the carbon-based nanomaterial is erected on the substrate, and is in a state of being clustered in the alignment direction, or being dispersed on the substrate, or being disposed in parallel on the substrate. Not limited to this. 15 Furthermore, the lithographic technique of the prior art is applied, and in the state of covering the portion of the surface of the carbon-based nanotube material, the modification on the surface is defined by performing the aforementioned treatment, and further, it may be repeated. The foregoing operations are performed several times, depending on the location. This method is suitable for occasions where different positions on the substrate are handled differently when bumps are formed. 20 The carbon-based nanomaterial in the month of the month is composed of at least one of a carbon-based nanotube material and a graphite sheet material. That is to say, it includes a sadness composed of only the incumbent, and also includes the composition of the two. This stone-soil material refers to a material in which a graphite sheet or a graphite sheet is modified by a certain meaning. Graphite sheet is called Graphene (graphite sheet) 19 200815282 5

10 15

20 or a substance called Graphene Nano-Ribbon, which typically has a nanometer-scale thickness (e.g., 〇·3ηηι~ hundreds of nm) ‘but in the industrial use field ‘there is also a larger scale. The graphite sheet is in the form of a sheet, and the carbon is located at the apex of each hexagon of the honeycomb shape, and is composed of a single layer or a plurality of layers, and may be rolled up into a cylindrical shape. If it is rolled up and connected to the crimped end, it is the structure of the nanotube. Graphite sheets can be produced by any method. The simplest method is to open the graphite sheet, but it can be produced by the same method as the carbon nanotubes by CVD or the like. Graphite sheet material, especially graphite sheet, has a unique layer of graphite shell sheet material if the number of layers is too large, such as the surface of the high-quality surface of the tooth, the conductivity and the anisotropy of conductivity. It is close to the graphite structure, and the characteristic anisotropy on the graphite sheet is reduced. In general, the number of layers in the thickness direction is from 1 to 10 layers, and is often referred to as a graphite sheet. The length and the width of the thickness are not particularly limited, and may be appropriately selected depending on the application, and are generally in the range of 0.3 nm to several hundreds nm. "妷糸奈管系材料" means a material in which CNT or CNT has been modified by some intention. Typically, the CNTs of the nanotubes having a nanometer-scale cross section (e.g., a face diameter of 〇.3 nm to 2 Gnm). The length may be an example of a few tens of Xinjiang, but there is no special limitation. The CNT has a block k which can satisfy the conditions for displaying the properties of the metal, and the wire can satisfy the (four) branch conductor (semi-metal). The bump structure of the nature strip & As the Cnt of the present invention, any one which exhibits metallic properties and exhibits semiconductor properties can be used. Further, the case where the graphite sheet is modified means that the metal is semi-metallic. The "Carboniferous Nanotube System Material" in the Ming Dynasty also contains the peapod structure of the 200820282 peapod structure, that is, the whole body contains metal fullerene ( Metal properties such as fullerene), and other nanostructures different from the nanotubes are accumulated in the CNTs. That is, the "modification" in the foregoing also includes such a form. 5 The electrical conductivity or mechanical strength of, for example, a via hole can be enhanced by using a nanotube tube comprising a pea pod having other nanostructures as described above. For example, a cNT containing a fullerene containing a metal has a charge which appears on the outer side of the fullerene and appears on the outer side of the nanotube. This is calculated by the first principle, thereby improving the through hole. Electrical conductivity characteristics. 10 For example, fullerene containing metal, which exhibits metallic properties in its entirety, and other structures or molecules or atoms different from the nanotubes, may not exist in the nanotubes but exist in a composition Between adjacent nanotubes of the through hole. Further, between adjacent nanotubes containing metal fullerenes, other structures, molecules or atoms different from the above-mentioned nanotubes may be disposed. Thus, the modified aspect of the CNT is also the "breaking nanotube material" in the present invention. The formation of pure carbon nanotubes such as CNTs, and (4) the use of arc discharge and laser-burning materials. At present, the company also produces Vd (chemical vapor deposition (IV) CVD. Since the CVD axis method can be directly on the substrate The upper shape is such as a nano tube. Therefore, it is expected to be applied to the manufacture of an integrated circuit. Of course, the CNTi manufacturing method used in the present invention is not limited. The carbon-based nano tube material of the present invention is mostly The occasion should be as described above, the end of the material, the material grows on the substrate, the smear, the nano tube system material grows on the substrate. The matter itself is not a must for the invention. 200815282 The condition is, however, when the carbon system is used as the official material. When growing on a substrate, as described above, it is easy to directly receive VUV irradiation, and the adhesion to the substrate is good, so that it is preferable. When the carbon-based nanotube material of the present invention is produced by CVD. The material for forming the substrate is not particularly limited, and a conventional material can be suitably selected. When it is desired to obtain conductivity, it is preferable to use a conductive material, and when heat conductivity is desired, it is preferable to use a heat conductivity. 15 20 In the present invention, The apparatus for irradiating the carbon-based nanotube material with a vuv and supplying a specific substance is not particularly limited, and may be, for example, a device having the structure shown in Fig. 2 and Fig. 3. In Fig. 2, in the vuv The source and the lower portion of the 21 are provided with a supply line for the gas 22 diluted with the inert substance, and a blowout port 24 for the specific substance. The source 21 is cooled by the cooling medium 25. X' is at the outlet 24 In the lower portion, the substrate 27 having the longitudinally aligned CNT bundles 26 is moved to the right from the left side of the drawing. In Fig. 3, the medium is replaced by a water-cooled tube 31, and the reading substrate 27 is smeared by a material dilution. The gas 22 after the substance is moved in the supply line 23, and the rest is the same as in Fig. 2. Further, the 'longitudinal arrangement of the coffee beans ^ can be realized by using, for example, a CNT bundle grown in the through hole. The arrow "indicated by the solid line in the 2nd and 3rd drawings" indicates that the gas after the specific (4) is diluted with the inert substance: the flow of the medium 25 for cooling, and the arrow of the dotted line indicates the projection of the vuv. According to the present invention, When bonding with other materials, the new carbon-based nano-materials are introduced. The material is suitable for use in the electronic delivery member 2, and the "affinity improvement" of the present invention is as follows: the surface tension k with the material contact, the improvement of the job, the improvement of the adhesion, the increase of the adsorption amount, 22 200815282 The meaning of foreign matter (water, etc.) and void (small space) between the layers of other substances is reduced. The "other substances" at this time should be selected from conductive substances, insulating substances, and hydrophilic substances. At least one of a group consisting of a lipophilic substance and a substance having a specific group. When a carbon-based nanomaterial is used as a material for the 4th electronic device 4, the material for the material can be used for a long time. The electrical connection of the components 'thermal connection, mechanical connection, solvent and adhesive>, moisture resistance, etc., can avoid defects such as peeling and wire breakage caused by long-term use. Further, in the description of the present invention and the description, "specific group", "specific substance", "specific structure", "specific solvent", "specific bond" 10, and "specific material" "Specific" does not mean something that is a fixed decision, but means that it can be arbitrarily determined according to practical needs. Such a conductive material may, for example, be copper, aluminum or another electrically conductive substance such as a metal used in the electronic wiring portion, and as an insulating material, generally, s〇G, Any of the semiconductor sealing insulating resins such as TE〇s (tetraethoxydecane) and 15 polyimide resin, or the most recently used micropores or micropores, which is called "Low- K resin (NCS, SiLK, MSQ, etc.) (many Si element), or fluorine resin such as PFA, FEP, Teflon (registered trademark), etc., that is, suitable for fixing the electrical properties of CNT bundles The insulating material, in addition, the hydrophilic substance may, for example, be an alcohol-based solvent such as water, ethanol, decyl alcohol, phenol, diterpenoid, ethylene glycol, diethylene glycol, triethylene glycol or glycerin. Further, the lipophilic substance may, for example, be a paraffin-based solvent such as petroleum ether, n-hexane or cyclohexane, or an aromatic solvent such as benzene, toluene, monophenyl or decylphenol, or THF (tetrahydrofuran). , DMF (-mercaptocarboxamide), DMs〇 (diterpenoid), dimethylacetamide, 23 200815282 or 2 a ketone such as a ketone or MIBK (methyl isobutyl ketone), and a heterogeneous element (such as C, 0 or oxime) containing n-methyl quinone, dichloroethane, dichloroethane or pyrimidine. Polar solvent. Further, the substance having a specific group is basically a substance containing a functional group of the insulating substance, the hydrophilic substance, or the 5-lipophilic substance (preferably a low-viscosity gas or liquid). Any one of the typical examples may, for example, have -OH, -COOH, COOR, -NH2, -NR2 (R is a month group, an aromatic alkyl group or a derivative thereof), -CO-, -C=0, At least one of an imide linkage and an ether linkage, that is, an alcohol and a phenol, a carboxylic acid, an amine, a ketone, and a benzophenone. 10 The carbon-based nanomaterial of the present invention can be used for electrical products, electronic products, mechanical products, etc., and can be used for carbon-based nano materials or for any use, and in view of carbon-based nanoparticles. The superior electrical and thermal properties of the material are particularly suitable for medical, aerospace or portable electronic devices that generate electromagnetic waves (including mobile phones, computers, etc. carrying 15' electronic machine terminals), or Electronic components and electronic devices (such as semiconductor devices and semiconductor integrated circuit devices including printed wiring boards). In addition, it can be used as an electroconductive member (sheet or the like), an electromagnetic wave shielding member (sheet, etc.) used in an electronic device that requires high performance, light weight, and little deterioration during long-term use, or can be peeled or broken. Electronic components and 20 electronic devices with few undesirable conditions. Further, such an electronic component may be, for example, a heat dissipation bump for mounting an electronic component, a wiring through hole for an electronic component, a gate electrode for a transistor, a source electrode, a drain electrode, a channel electrode, or the like. Further, the present invention is not limited to the above-described electronic components, electronic components, and the like, and may be an electronic device that requires a relatively high weight conductivity and heat transfer property (plane 24 200815282 or curved surface). Medical equipment, or high-frequency electromagnetic shielding materials for electronic devices, conductive sheets, and electronic terminals that generate electromagnetic waves, such as mobile phones and computers, and precursors used in the manufacture of the above-mentioned components (including so-called prepregs) . Fig. 4 is a cross-sectional view schematically showing a semiconductor integrated circuit device in which a carbon-based nanotube material of the present invention is applied to a wiring via of an LSI. In Fig. 4, a plurality of elements such as a plurality of transistors 42 are embedded in the germanium substrate 41, and a plurality of insulating layers covering the elements are formed (interlayer insulating film 〜43) is disposed at the germanium insulating layer, and is predetermined The wiring layer of the wiring layer is connected to the wiring 45 of the other layer by the through hole 46 formed through the insulating layer. 47 indicates the contact member connected to the wiring 45 of the connection element group. The upper wiring layer Covered by a protective layer 48. As shown in the figure, the device is applied by using the broken nanotube material of the present invention: U 岐 钱 钱 对于 对于 对于 对于 对于 对于= Insulating resin such as s〇G in a specific solvent:

^ permeability, from the material; can be blocked and fixed, so ώ ~ 丨 且 且 且 CNT CNT carbon nanotubes material upper end, ground cut into the through hole connection. Good electrical properties of the common wiring part 20:==: Material properties • (4) The structure of the high-performance electronic components: the meter tube is applied to the carbon-based nano-materials of the invention. 'At this time' can be placed on the block material. m, for several months, the cooling of the electronic components is carried out in the presence of a gas diluted with nitrogen by nitrogen or a gas diluted with nitrogen and nitrogen in the presence of nitrogen, and the substrate with CNTs in Fig. 5 is subjected to VUV treatment, and then, by plating (wet processing) the CNT portion on the CNT-containing substrate that has finished the treatment, it is possible to sufficiently penetrate the heat and electricity in the space between the cnt bundles. Conductive substances (gold, 5, etc. of Cu, A1, etc.), the so-called CNT hybrid bump structure. Thereafter, the electronic component can be heat-pressed (preferably from about 250 ° C to about 4501) on the substrate on which the above treatment has been completed. A highly thermally conductive electronic component using a CNT bump which has been impregnated with metal or the like can be produced. Fig. 6 is a schematic view showing a sheet for electromagnetic wave shielding or a prepreg 10 of the present invention. That is, the CNTs can be spread on the resin sheet, and the sheet can be bonded to other resin sheets to obtain an electromagnetic wave shielding sheet or a prepreg sheet. Example 1 As a substrate, it was used on a p-type (1 Å) surface of a Si wafer, and 25 nm of Ni was formed by sputtering, and acetylene was used as the original 15 by the filament CVD method. The multilayer carbon nanotubes were grown to a length of about 1.5 μm at 650 °C. The surface density of the nanotube was measured to be about 5 χ 10 π/cm 2 . 40 〇 in the clean air beforehand. (: The sample was fired for 15 minutes, and the flammable impurities other than the nanotubes in the surface of the nanotube were removed, and then quickly transferred to the treatment apparatus of the present invention, and the vapor pressure was 1 gas 2 The pure gas of about 5 vol% is diluted to dilute the gas which is a specific substance of the present invention, that is, triethylamine {N(CH2CH3)3}. The gas flow rate is 1 L per minute. In this state, Xe quasi can be produced by using An output of a molecular UV lamp (having a central wavelength of A = 172 nm) of 30 mW/cm 2 and an emission length of 4 〇〇 nm was irradiated with VUV for 10 minutes. The structure of the apparatus was as shown in Fig. 2. 26 200815282 by XPS (X-ray photoelectron spectroscopy) and IR (infrared absorption) spectroscopy analysis of the sample after the treatment of the sample, 'Surely tolerate the carbon and nitrogen bonds that are not present in other nanotubes, and then formed after treatment. Except for the point where VUV irradiation was not performed, the same points as described above were carried out except that carbon-nitrogen bonding did not occur after the treatment. Example 2 - Using the same specific substance as in Example 1 On the φ {p-type (100) plane of the Si wafer, it is grown by arc discharge method. Layers of carbon nanotubes are based. The same treatment as in Example 1. However, the processing time-based embodiment of the i ιοο 10 / 0〇

It was analyzed by XPS (X-ray photoelectron spectroscopy) and IR (infrared absorption) spectroscopy to confirm the carbon-nitrogen bond which was not present in the nanotube before the treatment, and was formed after being treated. Example 3 15 The same specific substance as in Example 1 was used, and an attempt was made to amination of a multilayer carbon nanotube having a through-hole structure in which a Φ transistor was formed. A cylindrical hole pattern having a diameter i〇〇nm and a depth of i〇00 nm is formed on the Si substrate, and a T11 film of 1〇11111 is formed by sputtering on the entire wafer including the bottom surface, and DMA (microparticle generation) is formed. The Co micro and 20 particles having an average particle diameter of 10 legs were spread over the entire wafer surface including the bottom surface, and a multilayer carbon nanotube having a length of 1500 nm was grown to a position above the hole by heat cVD &amp; The surface density of the nanotubes was determined to be about 3 xi〇u/crn2. The same apparatus as in Example 1 was used for the sample, and the same specific substance as in Example 1 was supplied, and νυν was irradiated in the same manner as in the Example. 27 200815282 A 1% ammonia water was dehydrated from the treated sample. After a while, it was sufficiently dried by a hot plate and observed by a scanning electron microscope (SEM) to confirm that the nanotube group was partially bundled in the hole. . This can be considered as a trace of ammonia soaking. That is, it can be considered that since the wettability with respect to the ammonia water is good, the ammonia water is wet on the surface of the nanotube, and the nanotubes are bundled by the ammonia water, and the ammonia water evaporates. On the other hand, after the same treatment was carried out on the nanotube specimen in the untreated pore pattern, it was confirmed that there was not much change before and after the treatment, and the nanotubes were almost not bundled and erected separately in isolation. That is, the nanotubes before treatment have a poor wettability, and the ammonia water is bounced back by the nanotubes. As a result, the nanotubes are not hunted by ammonia to form bundles. Then, the samples were cut out from the samples before and after the treatment, and the samples were analyzed by XPS (X-ray photoelectron spectroscopy) and IR (infrared absorption) spectroscopy to confirm the presence of carbon-nitrogen bonds in the nanotubes before the treatment. After processing, it is formed. From the foregoing results, the nanotube system is improved in hydrophilicity, and exhibits good affinity for a hydrophilic solvent, an adhesive, and the like. Further, in the present embodiment, the electric resistance between the upper side of the CNT and the lower side (substrate) surface formed by the ammonia water is an extremely low value of 2 Ω (ohm). 20 Example 4 Using the same processing system as in Example 1, a multilayer carbon system having a wiring via hole structure (measured in an areal density of about 5 x 1 根 根 / cm 2 ) of a transistor was formed in an analog manner. The nanotubes are carbonylated and hydroxylated. However, instead of triethylamine, oxygen diluted with N2 and h2 hydrazine may be used as a reactive substance. 28 200815282 A cylindrical hole pattern having a diameter of 2〇0ηΠ1 and a depth of 1000 nm is formed on a Si substrate, and a film of 1〇11111 is formed on the entire wafer including the bottom surface by sputtering, and DMA (Microparticle Generator) is used. Co particles having an average particle diameter of 7 nm were dispersed on the entire wafer surface including the bottom surface, and a multilayer carbon nanotube having a length of 5 500 nm was grown to a hole above the hole by a CVD method, and the same method as in Example 1 was carried out. In the method, the sample is subjected to carbonylation and hydroxylation. A gas containing 0.2% by volume of pure oxygen and remaining nitrogen was used as a gas containing a specific substance, and the gas flow rate was 3 L per minute. The apparatus was the same as that of Example 1, and the vuv was also irradiated in the same manner as in Example 1 10. The reaction time was 15% of Example 1. To the treated samples, ethanol, MIBK (mercaptoisobutyl ketone) and a one-to-one (volume ratio) mixture of the above were dropped, and after ten minutes, the plate was sufficiently dried 'by scanning electron microscope (SEM) Observation was carried out to confirm that in any of the samples, the nanotube group was mostly bundled in the pores. The ratio of bundled cNT 15 is the ratio of ethanol > one to one mixture &gt; MIBK (mercaptoisobutyl ketone). This is considered to be a trace after permeation of each liquid mixture, as in the case of the aforementioned ammonia water. That is, it exhibits good wettability to the aforementioned medium. On the other hand, the same treatment was applied to the nanotube specimens in the untreated pores, but only a very small number of nanotubes could be seen as 20 bundles. After that, each tube was cut and analyzed by xps (x-ray photoelectron spectroscopy) and IR (infrared absorption) spectroscopy to confirm that there was only a very small amount of 00 bond and _〇 in the nanotube before treatment. H-bonding, but after treatment, it was confirmed that each formed about 10 times (corresponding to the number of bonding moiré). 29 200815282 From the above results, the hydrophilicity of the nanotubes to the polar substance is improved, and the material having a C=0 bond and an -OH bond, an adhesive, etc., exhibits good affinity. [Example 5] By the same VUV treatment method as in Example 4, when the structure of the through-hole structure was formed by introducing the 〇=〇 bond sister and the -OH bond to the surface of the nanotube tube, the copper plating was performed. The Cii seed layer was previously seeded in an aqueous solution for plating a seed layer formation to be pretreated. Specifically, in the same manner as in Example 4, a multilayer carbon nanotube prepared by the same method as in Example 4 (measuring the areal density of the nanotube, about 5 χ 10 η/cm 2 ) The VUV treatment was carried out for 3 〇% of the time of Example 1, and then, the kCu plating seed crystal aqueous solution was immersed for 1 Torr. Observed by optical microscopy, SEM (scanning electron microscope), TEM (transmissive electron microscope), and EDX, almost all of the CNTs were bundled in a bundle, and a large amount of Cu fine particles were attached to the surface. Further, when a Cu film is formed into a thick film, a CNT-Cu composite in which Cu is adsorbed on the surface of the CNT is formed. On the other hand, as a comparative example, it was immersed in Cu plating seed water &gt; gluten solution for 1 未 minutes without performing a vuv treatment, and was observed by an optical microscope, and 20 CNTs were only partially bundled, and crystal The soaking of the seed liquid is not performed uniformly. Further, observation by SEM (scanning electron microscope), TEM (transmission electron microscope), and EDX, the Cu seed layer was adsorbed only on the bundled portion, and the sample was not able to form an equal Cu deposit layer. . Example 6 30 200815282 When a prepreg having CNTs grown on one side of a resin surface was produced, the CNT layer was applied to the inside after the VUV treatment, and a planar or other shape was formed. Specifically, according to S1 of Fig. 6, &lt; is pre-grown, and 400 in clean air. After roasting for b minutes, the flammable impurities other than the nanotubes on the surface of the nanotubes were removed, and then placed in methanol for ultrasonic treatment for two hours to prepare a uniformly dispersed liquid. This liquid was dispersed and dispersed in a flat ABS resin sheet (thickness 〇 5 mm) at a density of 1 mg/cm 2 to 6 Torr. (: It was allowed to stand to dry and remove methanol. According to S2 of Fig. 6, the VUV apparatus used in Example i 1〇 was used for treatment under oxygen diluted at n 2 (〇·5 vol%). The gas flow rate was 10 L/ In accordance with S3 in Fig. 6, it is placed on a flat ABS resin sheet (thickness 〇 5 mm) and placed at a temperature lower than the melting point of the resin sheet, and pressed for 5 minutes. In this way, a prepreg sheet of a conductive sheet or an electromagnetic wave shielding sheet can be obtained. Here, an example in which CNT is fused to an ABS resin is exemplified, but a resin and a modified resin may be applied. Then, for example, it is also possible to disperse and process CNTs on a sheet having a small shape retention and a general prepreg state. It is also applicable to all resins containing a thermosetting resin in a resin. As long as it does not scatter during CNT curing, the forming method is also applicable to various methods. Example 7 Substituting the nanotube on the Si wafer, using a single layer of graphite with a longitudinal direction of 2 〇〇# spot and 800/zm in the transverse direction Sheet, the sheet is placed in clean air and fired at 31 200815282 400 ° C After 15 minutes, and removing the flammable impurities other than the graphite sheet in the surface of the graphite sheet, it was quickly transferred to the treatment apparatus of the present invention, and pure nitrogen having a vapor pressure of 1 vol. To dilute the gas which is a specific substance of the present invention, that is, triethylamine {N(CH2CH3)3}. The flow rate of the gas 5 is 1 L per minute. - In this state, a Xe excimer UV lamp can be produced (to generate a central wavelength) λ = 172 nm) output 30 mW/cm2, excimer UV lamp with an emission length of 4 〇〇 nm, and irradiated with VUV for 10 seconds. The structure of the device was as shown in Fig. 2. By XPS (X-ray photoelectron spectroscopy) And IR (infrared absorption) spectroscopy 10 analysis of the sample before and after the treatment, confirming that there is no carbon-carbon bond in the nanotube before the treatment, and after treatment, it is formed. In addition, except for the point where VUV is not irradiated, The same treatment as described above was carried out except that carbon-nitrogen bonding was not produced after the treatment. Example 8 A graphite sheet (only 5 layers) prepared in the same manner as in Example 7 was used. 7 The same method, the hydroxylation of the graphite sheet. Diethylamine was carried out by irradiating vuv light with a volume fraction of 0.5% oxygen and 10 ppm of water vapor under a dry nitrogen atmosphere. Compared to the samples, a mixture of 2〇1 and 1 was dispensed with ethanol right. , MIBK (methyl isobutyl ketone) and its UV-free, no difference in wetness

32 200815282 The &amp; key, ,, and . And -OH bonding, forming a considerable amount after the reaction. In the embodiment 9, it is. When using various materials and carrying out the treatment in the same manner as in Example 8, it is necessary to push down the various functional groups which are slightly displayed in Fig. 8 and introduce them into the remainder of the outline of the figure. . Moreover, the use of oxygen as one of these substances, as shown in Fig. 8, will produce new defects, and the place can also be introduced into various industries for availability 10 15 20 (for example, When using materials that are incompatible with the system, when the materials are joined, the "member domain", and "the carbon-based nano-tube system materials" are other novel carbon-based nanotubes. * . [Jing Shan]: A schematic cross-section of a wiring through-hole structure using CNTs. Fig. 2 is a schematic view showing the main part of the vuv ^ for irradiating the present invention. The W material 3 diagram shows other schematic views of the main part of the device for illuminating the vuv of the present invention. Fig. 4 is a view schematically showing a cross section W of a semiconductor integrated circuit device in which a carbon nanotube of the present invention is used for a via hole. Fig. 5 is a schematic view showing an outline of an electron element including a high thermal conductivity bump which is used for a cooling bump material of a high functional electronic component. The above. /, Material: Fig. 6 is a schematic view showing a carbon-based nanotube system of the present invention; and an outline of the production method when applied to an electromagnetic wave shielding material. g糸Materials 33 200815282 Figure 7 is a schematic cross-sectional view of an untreated graphite sheet. Figure 8 is a schematic cross-sectional view of the treated graphite sheet of the present invention. [Main component symbol description]

1.. Substrate 2.. . Base layer 3.. .Cu wiring layer 4.. .Ta film 5.. Insulation layer 6...Ti film

7.. Catalyst metal film 8 ... CNT 9.. Filling resin 21 •••VUV source 22...gas after diluting a specific substance with an inert substance 23. Supply line 24:. Cooling medium 26· &quot;CNT bundle 27.. Substrate 31.. Water-cooled tube 41.. 矽 Substrate 42.. Transistor 43a to 43f... Interlayer insulating film 45·.·Wiring 46.. Through hole 47.. Contact member 48.. Protective layer 51.. Substrate 52.. Electrode 53.. Catalyst metal mounting film, catalytic metal film

54.. .CNT 34

Claims (2)

200815282 X. Patent application scope: The manufacturing method of the surface type «carbon system nano (4) is the surface modification and consists of at least carbon-based nanotube material and graphite sheet material. The manufacturing method is a method comprising the following materials: a stone & 糸 管 管 及 及 石墨 石 & & & & & 石 石 石 石 石 石 石 石 石 石 石 糸 糸 糸 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知Vacuum ultraviolet light; and The material modified by the surface of the rice material - 2.: The method for manufacturing the surface modified carbon system (four) material, wherein (4) the surface of the slave tree can be changed (4), the f system can be activated by vacuum ultraviolet recording. Those who produce chemically active species. The method of manufacturing the carbon-based nanomaterial of the surface of the first or second aspect, wherein the carbon-based nanomaterial to be modified is obtained by a CVD method. 4. The method for producing a surface-modified carbon-based nanomaterial according to the first or second aspect of the patent, wherein the carbon-based nanomaterial of the surface to be modified is grown on a substrate. 5. 2 Please apply the surface modification of carbonaceous nanomaterials in the first or second patent range = the chemically active species in which the aforementioned chemically active species contain electron-donating groups, and the chemistry of electron-withdrawing groups. At least one of the active species. 6. II. The surface modification of carbon-based nanomaterials in the first or second aspect of the patent scope, the method of modifying the surface of the carbon-based nanomaterials may be selected from the group consisting of oxygen And at least one of the group consisting of amines, halogenated alkanes, alcohols, ethers, and mixtures thereof. 7. The method for producing a surface-modified carbon-based nanomaterial according to claim 1 or 2, wherein the surface-modified substance of the carbon-based nanomaterial is diluted with an inert substance, and the inert substance The surface of the carbon-based nanomaterial is not modified by longitudinal or irradiation of the aforementioned vacuum ultraviolet rays. 8. A surface-modified carbon-based nanomaterial produced by the method of manufacturing a surface-modified composite nanomaterial of claim 1 or 2. 9. The surface modified carbon nanotube material according to item 8 of the patent application, which is selected from the group consisting of a conductive substance, an insulating substance, a hydrophilic substance, a lipophilic substance, and a substance having a specific group. When at least one of the constituents of the group is in contact, the affinity is presented before the surface modification. 10. An electronic component comprising the surface modified metabolite nanomaterial of claim 8 and 11. The electronic component of claim 10, wherein the electronic component is a through hole, An electronic component heat-dissipating bump, a conductive sheet, a sheet for electromagnetic wave shielding material, or a prepreg for manufacturing the sheet. 12. An electronic device comprising a surface-modified carbon-based nanomaterial of claim 8 of the patent application. 36