TW201135756A - Method for manufacturing carbon nanotube composite conductive film combined with metal nanoparticles - Google Patents

Abstract

A method for manufacturing carbon nanotube composite conductive film combined with metal nanoparticles, including the following steps: Firstly, manufacturing carbon nanotube composite combined with metal nanoparticles, and mixing carbon nanotube composite into a predetermined solvent to produce carbon nanotube composite solvent blend. Then, applying an ultrasonic atomizing frequency to make carbon nanotube composite solvent to release a plurality of atomized granules with carbon nanotube composite, and providing carrying gas to transmit atomized granules along a pre-determined path, so that the atomized granule is guided to the top of the base where the substrate is placed. By turning the base, the atomized granules will form uniform conductive film on the surface of the substrate. Finally, the conductive film is carried out microwave processing and the electrical conductivity and light transmittance can be improved.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a conductive film, and more particularly to a method for producing a conductive film of a carbon nanotube composite incorporating metal nanoparticles. [Prior Art] With the wide application and development of LCD screens, the development of transparent conductive materials has been a hot research topic. The transparent conductive films applied to displays and touch panels should have the following basic characteristics: (1) Light in the visible range Both transmittance and conductivity are high, (2) must be made into a smooth surface film, and can withstand the plasma process environment, (3) easy to touch to form a predetermined pattern, (4) large area uniform (5) low production cost (6) non-toxic and can be recycled. Indium tin (indium tin, hereinafter referred to as ιτ〇) has become a major source of transparent conductive film due to its low film resistance and visible light transmittance of ～9Q%. The = is a rare metal's limited production, resulting in unstable supply and a two-liter increase in raw material costs. Therefore, the development of new alternative materials has become a major issue. In addition, the touch panel and the flexible panel, which have been actively invested in the industry in recent years, are not sufficiently soft by the film, and have the disadvantages of relatively low (four) properties and relatively low reliability in use. In view of the lack of sources of bismuth and the application of its limits, Code: A popular alternative developed recently:: Two carbon nanotube materials have many excellent optical, electrical, magnetic and 疋 疋 巨 巨 巨 巨The nature and the microscopic _sheng of the material itself and its number of Baxing are directly related to the 201135756 series, which can affect the applicable product end. Currently, single-walled carbon nanotubes (single) that can be put into commercial application have been developed. -walled carbon nanotubes, abbreviated as SWNT) conductive film. The single-walled carbon nanotube conductive film is mainly made by a filter method and a spray method. Among them, the filter method is to first synthesize SWNT by laser, pickle it with a high concentration of nitric acid solution, add it to a solvent containing a specific surfactant to form a carbon nanotube solution, and then filter it with a specific filter paper. The carbon nanotubes are parked on the surface of the filter paper to form a carbon nanotube membrane, and then the carbon nanotube membrane is transferred to a transparent substrate, and the filter paper portion is removed by acetone, leaving only the carbon nanotubes. A single-walled carbon nanotube conductive film can be produced ("Transparent, Conductive Carbon Nanotube Films,, J Z. Wu etc., Science 2004, 305, 1273 ' ^Effect of SOC12 Treatment on Electrical and Mechanical Properties of Single- Wall Carbon Nanotube Networks", U.Dettlaff-Weglikowska etc., J. Am. Chem. Soc., 2005, 127, 5125-5131). The method for preparing a single-walled carbon nanotube conductive film by spraying is A predetermined amount of single-walled carbon nanotubes is added and dispersed in a solvent containing a specific surfactant to form a carbon nanotube solution, and after centrifuging the carbon nanotube solution, a 50% partial spray of the upper layer of the solution is taken. Sprinkle on surface temperature dimension On a poly(ethylene terephthalate, abbreviated as PET) substrate at 100 ° C, followed by washing with deionized water and drying, a single-walled nanocarbon can be obtained. Tube conductive film ("Effect of Acid Treatment on Carbon Nanotube-Based Flexible Transparent Conducting Films 55, J. Syria CTzem. Soc., 2007, 129, 7758-7759). 201135756 In addition, although the carbon nanotubes themselves have excellent photoelectric characteristics, the contact resistance between the carbon nanotubes is still 1 to 3 times that of the single carbon nanotubes. Therefore, the above-mentioned single-walled carbon nanotubes The contact resistance of the conductive film between the carbon nanotubes is still the research focus of improving the conductivity of the conductive film. Although the academic and industry's active research and development, various transparent conductive films have been developed, and the manufacturing technology of the single-walled carbon nanotube conductive film has entered the stage of commercialization, and it can replace Ting Yu.

The trend of film, but the related process technology can not be successful in a short time: in response to future needs 'and create more humane interface products and soft electronic products' related to touch panels, flexible panels, The process technology of liquid crystal displays such as transparent electrodes will also be changed. Among them, the maturity of material technology will be a key element. Therefore, there is still a need to continuously develop different types of material technologies and improve the performance of existing materials, especially the light transmission plate. The electrical performance is the second major focus of the current research, which can further enhance the production of the second use of f, and more precise nin-cycle technology can effectively reduce production costs. SUMMARY OF THE INVENTION The process is relatively simple and capable of absorbing metal nanoparticles. Therefore, an object of the present invention is to provide a method for producing a conductive film of a carbon nanotube composite in combination with further improving light transmission and electrical conductivity. The invention relates to a method for preparing a special film, which comprises the following steps: (1) dissolving a predetermined amount of a metal salt compound in a solvent to prepare a 坌 w, ★ Li Fei Cold-made "a" trough liquid" and dissolve a predetermined amount of carbon nanotubes in - water, organic solvent or eight private V * as a dispersion, and then mix and stir the mixture, 201135756 The predetermined heating rate is raised to (10) t~16 Gt and maintained for n-stage to form a plurality of carbon nanotube composites combined with metal naphthalene; (9) adding a predetermined amount of carbon nanotube composites to a predetermined amount The solvent is mixed into a carbon nanotube composite solution having a viscosity value of UOc p; (111) 1⁄4 plus an ultrasonic atomization frequency in the carbon nanotube composite solution, so that the carbon nanotube composite solution Releasing a plurality of atomized particles carrying the carbon nanotube complexes and providing a carrier gas to cause the atomized particles to be transported along the predetermined (four) 'wafer' Μ // m~50 // m ; (iv) directing the atomized particles to - placed with - Above the susceptor of the substrate sheet, by rotating the susceptor, the atomized particles uniformly form a carbon nanotube composite conductive film on the surface of the substrate sheet; and (v) the carbon nanotube The composite conductive film is placed in a chamber for microwave post-treatment to enhance its light transmittance and electrical conductivity. The beneficial effects of the present invention are as follows: a carbon nanotube compound is combined with a metal salt compound to prepare a metal nanoparticle. The carbon nanotube composite film with better conductivity can be quickly heated and can quickly remove heat: the post-wave treatment can re-melt the metal nanoparticles to effectively adhere and fix The carbon nanotube wall overlaps, so that the invention can not only use ultrasonic atomization and spin coating, but also produces a film with better conductivity by simple equipment and process technology, and can also pass through the microwave. The treatment further improves the light transmittance of the conductive film and reduces the electrical resistance thereof. [Embodiment] The foregoing and other technical contents, features and effects of the present invention are combined with a reference pattern below 201135756. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A clear description will be given. Referring to Figures 1, 2 and 3, a preferred embodiment of the method for producing a carbon nanotube composite conductive film incorporating metal nanoparticles comprises the following Step: Step 101 is prepared by dissolving a predetermined amount of the metal salt compound in a dry ethylene glycol to prepare a first solution, and dissolving a predetermined amount of carbon nanotubes in an anhydrous ethylene glycol to prepare a first solution. The dispersion is mixed and stirred, and then rises by 2 per minute. (:~5. (: The temperature rise rate is raised to 1〇〇π~16〇.^ and the temperature is maintained for 1 to 3 hours to make the metal salt compound The metal ions in the metal are reduced to metal nanoparticles and adhered to the carbon nanotubes to form a plurality of carbon nanotube composites combined with metal nanoparticles, which are directly filtered while hot and ethanol-free. These carbon nanotube composites can be obtained by rinsing several times and vacuum drying at a temperature of 8 〇 β (:. The carbon nanotubes can be multi-walled nan〇tubes (MWNT) or single-walled carb〇n nan〇tubes (referred to as SWNT), which is used in this embodiment. Multi-layered wall carbon nanotubes. It is worth noting that the main control parameters in this step are the reaction temperature and the heating rate. The main features of using ethylene glycol as the solvent here are: (1) Ethyl alcohol itself is a solvent system with high viscosity, which is high. The polar characteristics help/cohesive; the metal salt compound is placed, and its high viscosity prevents the metal ions from diffusing, and the viscosity and the diffusion rate of the metal ions are controlled by the temperature rise, so that the generated metal nanoparticle suspension can be generated. The ratio in ethylene glycol or to the wall of the carbon nanotube tube. (2) Since the boiling point of ethylene glycol is 198 ° C, the solution of the 201135756 solution and the dispersion can be heated to a higher temperature to help reduce the metal ion having a higher activity to a zero-valent metal atom. For example, platinum ions must reach a high reduction ratio at 120 ° C, and silver ions need to be as high as 15 〇 β (: can achieve the same effect. (3) oxalic acid formed after ethylene glycol oxidation is also a good metal naphthalene The rice particle protecting group plays an important role in the particle size control of the metal nanoparticle and the stability of the metal nanoparticle before it is bonded to the carbon nanotube. However, the thermal decomposition temperature of the oxalic acid is 175t. Therefore, it is effective. The use of ethylene glycol and oxalic acid to reduce the ratio of metal nanoparticle aggregation to bare suspension, the reaction temperature should be lower than 175, and should be higher than 100t to facilitate the reduction of metal ions. Therefore, the final reaction will be heated in this step. The temperature is limited to loot ~160 ° C. In addition, the heating rate is the ratio of the particle size of the formed metal nanoparticle to the metal nanoparticle attached to the carbon nanotube compared to the amount of the original added metal ion. The faster the heating rate is, the smaller the particle size of the formed metal nanoparticles is, and the lower the ratio of adhesion to the carbon nanotubes is. The preparation of nano carbon combined with platinum and silver nanoparticles is prepared. For example, the tube composite is characterized by a slow rise in temperature per minute and a rise in temperature per minute, respectively. (: It is defined as a rapid temperature rise, and the temperature of the two-minute heating rate is obtained by the sister-incorporated metal nanoparticle. The nano-carbon nanotube composites were observed by transmission electron microscopy to show that the metal nanoparticles attached to the wall of the carbon nanotubes were dense, and the average (4) of the metal nanoparticles was 3 84 (10), and the actual particle size. The distribution range is from 2 nm to 7 nm. The thermal analysis results obtained by calcination show that the metal loading rate is 99% of the original metal addition, which fully shows the high ratio of metal loading. At a heating rate of 5 t/min. The prepared carbon nanotube composite with 201135756 metal nanoparticles was observed by a transmission electron microscope, and the density of the metal nanoparticles on the wall of the carbon tube was slightly lower than 2 C. Knife clocker X average of its metal nanoparticles The particle size is reduced to 3 〇〇 fine,

, continuous grain; U knife cloth range is enlarged to i nm ~ 7 nm, and _. The results of the thermal analysis obtained by 〇 〇 显示 showed that the metal loading rate was only 89/ of the original metal addition. Therefore, in the selection of the heating rate, it is necessary to cooperate with the subsequent application direction. When the catalytic or electrical conductivity is the main application direction, the slow heating rate of the metal natriene adhesion ratio is selected, and the transmittance or small particle is used. When the diameter is the main consideration, the faster heating rate is selected as the selection condition. Wherein the metal nanoparticles on the carbon nanotube composites are made of a metal selected from the group consisting of: 33, silver, gold, and the like; The metal salt compound is a material selected from the group consisting of potassium tetrachloropropanoate (K2ptCl4), silver tartaric acid (α_3), and tetrachloroauric acid (HAuC14). By using different metal salt compounds, a carbon nanotube composite combined with different metal nanoparticles can be formed, and the nanocarbon tube composite can be controlled by adjusting the ratio of the amount of the metal salt compound to the carbon nanotube. Medium = content of metal nanoparticles. The content of the metal nanoparticles in the nanocarbon carbon composite is preferably 10 wto / 〇 ~ 4 〇 wt 〇 / o. When the carbon nanotube composites have only one type of metal nanoparticle: as described above, a first mixture of the first solution and the dispersion is formed. After the liquid is applied to i 〇〇°c~丨6〇〇c and maintained at a constant temperature for a period of time, the metal ion in the metal salt compound can be reduced and cut off directly after the thermal transition. On the carbon nanotubes, a carbon nanotube composite having one type of metal nanoparticles is formed. 201135756 In addition, the carbon nanotube composites may have two or more kinds of metal nanoparticles, for example, when When the carbon nanotube composite has platinum and silver metal nanoparticles, the preparation method comprises the steps of: dissolving a predetermined amount of tetrachloroplatinic acid in anhydrous ethylene glycol to prepare the first solution, and then containing the naphthalene The carbon ruthenium is mixed in a liquid phase to form the first mixed liquid, and is heated to a temperature of 2 °c to 5 ° C per minute by a rise of 2 ° C. After maintaining the constant temperature for 2 hours, the platinum ion can be Reducing to platinum nanoparticle and respectively bonding to the carbon nanotubes, at this time, first cooling to room temperature, and then adding a second solution to the first mixture to form a second mixture, the first The second solution is prepared by dissolving a predetermined amount of silver tartaric acid in anhydrous ethylene glycol. After the second mixture is dropped, it rises by ~5 per minute. (: The temperature rise rate is raised to i〇(rc~i6(rc) and the constant temperature is maintained for a period of time, so that the silver ions in the silver nitrate are reduced to Silver nanoparticles are bonded to the first nanoparticles to form a carbon nanotube composite with platinum and silver nanoparticles. Due to the interaction between the silver particles and the carbon nanotube wall The adhesion is not as good as the adhesion of the surface nano particles, and the price of the starting material is close to 1 times that of silver. In order to increase the commercial and practical price of the carbon nanotube composite in the conductive product, a small amount of the first is won. The sub-bonding to the carbon nanotubes 're-transfers the silver ions to the carbon nanotubes through the Mingnai particles. Therefore, by using the two kinds of gold particles, the metal nanoparticles can be attached to the naphthalene. The pre-product of the carbon tube can also reduce the cost of raw materials. Among them, the weight of rice particles and silver is compared...: 5~1:2〇. If the cost of raw materials is considered, it is better to be 1:1. The content of nano particles and silver particles in the carbon nanotube composite is (4) 2%, at 10 201135756 Under these conditions, the best loading efficiency (ie, the total metal adhesion rate is expressed as the ratio of the weight of the metal nanoparticles attached to the carbon nanotubes to the weight of the metal ions in the metal salt compound). Step 102 is to prepare a The carbon nanotube composite solution 30 is prepared by adding 1 part by weight of the carbon nanotube composite and 1 part by weight of the surfactant component to 1000 to 1,000,000 parts by weight of a solvent to a viscosity of 1 to 50 C.P. The carbon nanotube composite solution is 3 〇, and the above viscosity value is measured at room temperature. The source of the live biochemical component is used to prevent the aggregation of the carbon nanotube composites. Substances selected from the group consisting of sulfated alcohols (ROS 〇3-M+), alkyl sulfonates (RSI 3M), α olefins Acid salt (aipha-〇lefinsulphonate, abbreviated as A0S 'general formula is RCH=CH(CH2)n-S03M), fourth-order ammonium salt

(Quaternary amm〇nium sah, general formula), ethylene oxide (also known as 5 ^ ethyl alcohol - 'polyoxyethylene, abbreviated as POE), polyoxyethylene alkyl ether (also known as fatty alcohol polyoxyethylene ether, Alcohol ethoxylate, abbreviated as AE, has the general formula RO(CH2CH20)nH), and combinations thereof. Preferably, the surfactant is a substance selected from the group consisting of sodium linear alkyl sulfonate of C4~C丨8 (formula: RS〇3_Na+), linear alkyl sulfonate of C4~C18 Potassium acid (formula: rso3_k+), linear alkyl sodium sulfate of c4~c18 (linear hydroxy (VNa+), c4~C18 linear alkyl sulphate (formula of ROSO3 K), C4~C18 Direct-bonded benzoyl sulphate (formula RC6H4 11 201135756 SO3 Na ), C4~C!8 linear chain-based potassium benzoate (formula rc6H4 S03-K) C4~Ci8 direct key dazzle Basic sodium sulfate (formula R〇c6H4s〇3_Na+) C4~Cig direct-bonding basic sulfuric acid unloading (generalized as r〇c6h4|§C)3-k+), C2~C16 linear alkyl quaternary Ammonium salt, α-olefin sulfonate (abbreviated as A〇s, the formula is RCH=CH(CH2)n-S03M, where 'n=14~16, and Μ is the gold-requiring ion), and the alkyl group is C2 a polyoxyethylene alkyl ether of ~c16 (abbreviated as ΑΕ, a formula of RO(CH2CH20)nH, η=5~30), and combinations thereof. Thereby, a better dispersion effect can be attained. In the present embodiment, sodium dodecyl sulfate (SDS) is selected as the surfactant. Dan, the solvent is selected as 'isopropanol and acetone. In this embodiment, water is used as a solvent. Prepare £, add the nano carbon tube composite and the surfactant to the bath, and then use the probe type ultrasonic (four) disperser with power of 750W (model: & Materials' Inc. "Card like 8VCX75〇 The carbon nanotube (6) solution 30 was applied at 20% power for 5 minutes, and the 3% power action was applied to prevent the carbon nanotube composites from agglomerating and being uniformly dispersed. Step 1〇3 is to apply a _ultrasonic atomization frequency to the carbon nanotube complex solution 30 to atomize the carbon nanotube composite solution, and the above (4) ^ the carbon nanotube composite solution 3G will release a majority of the cockroaches with these = carbon tube composites (4) lions 31, and provide - carrying gas Μ to transport the granules 31 along a predetermined path. Wherein, the carbon nanotube composite liquid 30 is contained in an atomization by a siphon 34 maintained at a fixed level: 3:,: the liquid level of the solution is 3°, thereby generating the supersonic 12 The ultrasonic wave element 35 of the 201135756 wave frequency is constantly located at a fixed depth below the liquid surface to control the fixation of the energy of the liquid level of the solution, and the particle size of the atomized particles 31 produced can be maintained. The siphon tube 34 is connected between the atomization container 33 and a liquid storage container 38. The liquid storage container 38 is placed on a lifting base 3 to be vertically displaced by the parent, and the mist can be controlled thereby. The liquid level in the container 33 is still good. Preferably, in order to maintain the dispersed state of the carbon nanotube composite in the carbon nanotube composite solution 30 flowing to the liquid storage container, a probe is usually additionally installed in the liquid storage device 38. The ultrasonic oscillating diffuser (not shown) continues to act on the solution flowing back to the reservoir 38. In this embodiment, the ultrasonic atomization frequency of L65.MHZ is used (the super used in this embodiment) The model of the sonic atomizer is: 崴_ Wave Electron^ Corp M165D25, M165D2〇)' and the particle size of the atomized particles 31 is between 〇. 5 # m~5〇#m Preferably, it is between m and 7 . In the present embodiment, the particle diameter of the atomized particles 31 is substantially maintained at about 3 vm in accordance with the ultrasonic atomization frequency. In order to meet the required particle size, the frequency range of the ultrasonic wave can be estimated by the following formula to adjust to the required atomized particle size 31 more quickly:

(8πΤ V where D is the particle size of the atomized particles, τ is the surface tension coefficient (N/cm), P is the solution density (g/cm3), f is the ultrasonic atomization frequency, and 邙 is 〇·34 Ten value. (uitrasonics v〇lume 22, Issue 6, N〇vember 1984, Pages 259-260) 13 201135756 Preferably, the flow rate of the carrier gas 32 is 1 L/min~2〇〇L/min, in this embodiment In the example, the flow rate of the carrier gas 32 is set to 22 L/min ' and the carrier gas 32 is nitrogen. Step 104 is spin coating, and the atomized particles 31 are guided to a substrate on which a substrate sheet 36 is placed. Above the seat 37, by rotating the base 37, the atomized particles 31 such as Åhai are uniformly formed on the surface of the substrate sheet 3, and a conductive film 100 is uniformly formed. When the rotating cloth is rotated, the pedestal 37 is once passed once. The wet spin coating and the preliminary pre-film spin coating pretreatment, and repeated periodic re-filming spin coating, and in the re-film spin coating, sequentially through the low speed, one middle The rotation speed of the speed and the rotation of a high speed are rotated. In this embodiment, the low speed is preferably 3 〇〇 45 45 〇rp, the medium-speed rotation speed is preferably controlled at 450 to 900 rpm, and the high-speed rotation speed is preferably 〇〇6000 rpm·, wherein the rotational rotation coating is performed at a speed of 3 (10) rpm and 450 rpm. Then, the rotational speed of the preliminary film-forming spin coating is from the stepwise rise to 450 rpm from 450 rpm and then enters the periodic re-filming rotation. Step 105 is hot pressing, which is set at a predetermined temperature. The substrate sheet 36 having the conductive film 100 is applied with a predetermined pressure for compacting the conductive film 100 and forming a denser and stable structure, and forming a tighter structure between the carbon nanotube composites. The bonding helps reduce the surface resistance of the conductive film 100, so that the conductive film can exhibit better conductivity. Preferably, the hot pressing is performed at a temperature of 5 〇〇c to 丨1〇. Applying a hot pressing pressure of 1 to 200 kg/cm for 3 () seconds to 3 minutes, in this embodiment, 14 201135756, applying a pressure of 100 kg/cm 2 at a temperature of 70 ° C for 3 Torr, but This should not limit the hot pressing time. 'The longer the hot pressing, the more conductive. , But more than 30 minutes after the hot conductive but not significant improvement, the heat pressing time should be within 30 minutes.

Step 106 is cleaning. The substrate sheet having the conductive film 1〇〇 is firstly rinsed in deionized water for 5 to 30 minutes' and soaked for 2 hours for water exchange, repeated 5 times, and then soaked in ethanol for 2 hours, and then at temperature. A vacuum is applied under 6 〇〇c, whereby the surfactant remaining in the conductive film 100 can be removed to prevent the residual impurities from causing a decrease in the conductivity of the electrical film. After the completion and drying, the finished carbon nanotube composite conductive film 100 bonded to the metal nanoparticle is bonded to the substrate sheet 36. In addition to the only steps made, it is worth mentioning that in step • , ~, _, / L \JL factory / | teaching nano carbon tube complex with solvent blending for the carbon nanotube complex dissolved T a predetermined proportion of the pure carbon nanotubes of the unbound metal nanoparticles and the carbon nanotube composite combined with the metal nanoparticles may be mixed into the solvent to prepare a carbon nanotube composite solution, and In step ι 3, the atomized particles are simultaneously entrained with the carbon nanotube composites and the pure carbon nanotubes. By using the carbon nanotube composite with the best load efficiency and the carbon nanotubes, the expected conductivity can be achieved, and the amount of metal nanoparticles can be reduced to reduce the cost. _ When the tubes overlap, as long as the single-sided carbon nanotubes have metal nano- ΙΓ ΙΓ connected to the two nano-walls to reach a predetermined conductive channel, the conductive mixture of carbon nanotubes and pure carbon nanotubes Still able to reach 15 201135756 Step 107 is to place a plurality of substrate sheets 36 having the conductive film 100 in a chamber 41 of the microwave device 4 for microwave post-treatment to enhance the light transmittance and electrical conductivity. Since the melting point of the metal material is often much higher than the extreme temperature that the polymer flexible substrate (for example, the PET substrate) can withstand, the post-treatment method must be carried out under the process conditions that the polymer flexible substrate can withstand. Therefore, it is preferable to carry out post-treatment by a method capable of rapidly raising the temperature and rapidly removing the heat source, and on the other hand, by heating the carbon nanotubes

And the metal nanoparticles attached thereto can promote the adhesion of the metal nano particles to each other and enhance the adhesion of the metal-nano carbon tube wall interface. On the other hand, it can reduce the residual heat to the polymer through rapid cooling. Thermal destruction of the substrate. Among them, post-processing by microwave has practical value and economic benefits that can improve photoelectric efficiency and cost without expensive equipment. In the present embodiment, helium is subjected to a microwave heating (miCrowave heating) treatment in an environment having a pressure of 25 〇 t rr or more. The microwave heating treatment method has the characteristics of rapid temperature rise and rapid removal of the heat source, and the purpose of heating the molten metal nano particles can be reduced by rapid cooling to avoid the substrate sheet of the polymer material. 36 caused thermal damage. Since the microwave is a high-energy heating source, the processing time of the microwave post-treatment is preferably limited to 3 minutes. The microwave heat treatment method is further described below: Microwave heating: a substrate sheet 36 having a conductive film 1 置于 is placed in a chamber 41 of a reaction chamber 41 of the Depo device 4, and an evacuation unit is used. 42 is provided to the chamber 410 #vacuation, re-transmission-supply unit 43-selected from: gas 5 in the column group to the chamber 41G: nitrogen, argon, helium, oxygen, hydrogen, and air. The chamber 41 is maintained at a predetermined pressure. In the 16 35 施 16 2011 2011 2011 2011 2011 2011 2011 2011 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 惰性 16 惰性 惰性 惰性 惰性 仃 仃The microwave heating treatment is performed under normal pressure, which also improves the light transmittance and electrical conductivity of the conductive film 100. Wherein, the microwave unit 44 is continuously supplied with microwave energy for the predetermined period of time for a predetermined period of time, and the gas 5 is applied to the conductive film 1 through the gas 5. The power of the transmitting microwave unit 44 used in this embodiment is 75 〇 W ' and the frequency is substantially set to 2.45 GHz when used, and the source used is a magnetron. It is worth noting that after the microwave heat treatment is used to obtain the conductive thin film 16 with better light transmittance and electric performance, it can also be matched with a mask formed with a predetermined hollow pattern or circuit pattern (not shown). Covering the portion of the conductive film 1 ,, the region 'the microwave film is further subjected to microwave electric heat treatment, and the carbon nanotube composite conductive _ i (9) is not covered by the metal in the region not covered by the shielding member The portion of the carbon nanotube adsorbed or coated by the nanoparticle is subjected to microwave plasma, and the 'flying vaporization' forms a selective etching on the conductive film 100, and the region is formed into a region where the current cannot be conducted. The shaded area is formed by a circuit circuit diagram for conducting current. In this way, a pre-made circuit pattern can be generated on the 6-inch conductive thin crucible (10), which has the value of practical application. Among them, except for the pressure condition, the microwave plasma heating is similar to the microwave heating treatment described above, so when the microwave electric heating is not described again, the chamber 41G is first evacuated, and then the gas is supplied to the chamber. The pressure is maintained at 〇"_~2 〇t〇rr. &lt;Specific Example of Preparation of Nano Carbon Tube Composite Bonded with Gold Nanoparticles&gt; 17 201135756 150.2 mg of purified and heat-treated carbon nanotubes were dispersed in i QGml without using a solar wave in a nitrogen atmosphere. In the ethylene glycol solution, HAuCl4 (65 2 (4)), which has been fully dissolved in 10 (ml) of anhydrous ethylene glycol, is transferred to a water-containing ethylene glycol containing carbon nanotubes by a double-ended needle under a nitrogen atmosphere. In the dispersion, after sufficient (four) uniformity, the rc is slowly raised to 16GC' per minute and the reaction is terminated after 2 hours of strange temperature. The formed carbon nanotube complex A is collected by hot transition and rinsed with absolute ethanol. After several times, vacuum drying at 8 ° C for 12 hours, a carbon nanotube composite loaded with 2G wt% of gold nanoparticles can be obtained. Among them, the function of the above double needle is to allow two nitrogen rings * brother Next, the valley liquid system is effectively transferred from one side to the other side, and does not touch the outside work gas, for example, a needle for blood drawing, because the needle side is connected to the blood vessel, and the side of the ▲ bag is a kind of double-headed needle. As shown in the ® 5' for the carbon nanotube complex a After the step is made into a conductive film, the visible light optical error transmittance before and after the microwave heating treatment is measured, and the conductive film before the microwave heating treatment is displayed at a wavelength of 575 nm and has a surface electric characteristic representing the characteristics of the metal nanoparticle. The resonance absorption peak, that is, the appearance of the surface electrical resonance resonance absorption peak indicates that gold nanoparticles are indeed present in the conductive film, and accordingly, it can be reasonably estimated that the gold nanoparticle can be combined with the atomization treatment after being dispersed and atomized. There is an excellent adhesion between the wall of the shim knife carbon tube, which shows that it has excellent attachment force. Therefore, the surface can still be observed on the conductive film prepared by the carbon nanotube 1: material: Electropolymerization resonance absorption peak. According to this, the method of the present invention can also be explained::: (4) The composite can withstand the processing procedure of super-clear wave dispersion and atomization which is formed into a film, and can be smoothly produced into the 18 201135756 A carbon nanotube composite conductive film product. <Specific Example 2 - Preparation of a carbon nanotube composite conductive film incorporating gold nanoparticles> (1) Prepared in the manner shown by &lt;Specific Example 1&gt; 20 wt% of gold nanoparticles Tube composite A (in which the metal salt compound is HAuCU, the amount is 65.2 mg) is sample I. (2) The sample I is configured as a 10 mg/L carbon nanotube complex solution: respectively, in 1 L of deionized water. 10mg of sample I, II and 10mg of SDS can be first applied to the nano carbon tube complex solution with a probe type ultrasonic shock diffuser (model: Sonics &amp; Materials, Inc. "SONICS® VCX750") with a power of 750W. It was applied at 20% power for 5 minutes and 30% power for 5 minutes to prevent the carbon nanotube composites from agglomerating and being uniformly dispersed. (3) Atomization: The ultrasonic atomizer is placed at a depth of 3.0 cm below the liquid surface, and the temperature of the solution is maintained at 30 ° C, and an ultrasonic atomization frequency of 1.65 MHz is supplied to the carbon nanotube. The composite solution can reach an atomization rate of 25 to 3 〇 1111/111>, and the atomized particles have a particle size of about 3#111, and are delivered by a gas pipe connected to a container containing the sample I and II solutions. The carrier gas was introduced, and the flow rate of the carrier gas was 22 L/min. (4) Rotary coating: the carrier gas guides the atomized particles to the base of a spin coater, and the substrate sheet placed on the base is rotated synchronously with the base for spin coating Previously, the substrate sheet was washed with deionized water for 40 seconds at 500 rpm, and then washed with alcohol at 800 rpm for 60 seconds, and then spin coating of the ultrasonic atomized particles. 19 201135756 When spin coating of ultrasonic atomized particles, s Α ^ 疋 without a wet spin coating and a preliminary film-forming spin coating pre-emptive, Dan repeated multiple periodic re-filming Spin coating. Among them, whoever wet the spin coating speed is 300 rpm and 450r.pm alternately, the speed of the initial film-forming spin coating is increased from 450 rpm to 6〇〇〇rPm. Then enter the periodic re-filming spin coating. During the coating process, the susceptor is continuously rotated in a staged cycle as shown in FIG. 9, and the interval (I) represents the change in the rotational speed of the wet spin coating, and the interval (II) represents the preliminary film spin coating. The stepwise rotational speed change, the intervals (III), (IV), and (V) are all stepwise rotational speed changes of the re-filming spin coating, thereby enabling the atomized particles to be uniformly applied to the base. The surface of the sheet is controlled, and the film thickness of the carbon nanotube composite conductive film can be controlled by the length of time of coating. In Figure 9, the different stages are indicated by different letters, and the speed and time they represent are organized as follows! The time of each stage in the table] should be limited and can be adjusted according to actual needs.

The coating time of the square turn coating is controlled from 10 minutes to 6 minutes to control the spin coating time to achieve the design specifications of the multilayered wall carbon nanotube conductive film, mainly by The time of c~f was adjusted to adjust the thickness of the conductive film of the 5 Henne carbon nanotube composite. (5) Hot pressing: The temperature of the upper and lower stampers of a hot press is raised to 7 Torr. 〇, and maintain a constant temperature for 1 hour, and control the temperature up and down changes to ± 〇 25. 2020 201135756,&gt; Cut four Ji 5 cmx5 c_ PET thin μ, and rinse them in de-ionized water, deionized water, acetone, deionized water, and then each of the above two pieces. The method is to clamp the substrate sheet which has been provided with the conductive thin film (the knife is made of the mouthpiece I~[V], and then the cmxl〇cm stainless steel fixture is superposed on the PET sheet, and the combination is combined. The finished substrate sheet PET sheet was placed between the upper and lower stampers of the hot press together with the non-recording steel jig, and subjected to a pressure hot pressing of 10 kg/cm 2 for 3 minutes. + (6) Cleaning: The hot-pressed conductive film substrate sheet ' is cleaned in the manner described in the above step 1G6' to obtain a carbon nanotube composite conductive film 1 incorporating gold nanoparticles (made by the sample I) &lt;Changes before and after microwave heat treatment&gt; (1) Before microwave heat treatment: &lt;Specific Example 2: Preparation of carbon nanotube composite conductive film combined with gold nanoparticles&gt; The carbon nanotube composite conductive film of the gold nanoparticle is cut into several pieces of lcmx2cm test piece, and the visible light transmittance before the microwave heat treatment, the light transmittance at the wavelength of 550 nm, and the piece are measured first. (2) The test piece of the conductive film j is placed in the microwave device 4 as shown in FIG. 3 for microwave heating treatment under the conditions of a pressure of 25 〇t rr, a microwave action time of 90 seconds, and after microwave heating, The visible spectrum transmittance of the test piece of the conductive film j, the light transmittance at a wavelength of 550 nm, and the sheet resistance are measured. It is necessary to add a note to the gold in the test piece of the conductive film after microwave heat treatment. The particle size of the nanoparticles is still less than 1 〇nm, so it cannot Dream Scanning Electron Microscopy (SEM) is used to observe the actual shape change of the gold nanoparticles on the surface of the carbon nanotube wall, while the transmission electron microscope (referred to as 21 201135756 TEM) sample carrier (carbon coated copper) In the microwave environment, severe arc discharge damage occurs, so it cannot be observed by ΤΕΜ. Only X-ray powder diffraction spectrum (XRD) can be transmitted. The peak position (angle), the half-peak width value, and the Scherrer equation are used to calculate the particle size of the nanoparticle (BD Cullity, SR Stock, jE/emewb 4th, Chapter 5, Prentice-Hall (2001), C. Gervais, Μ. E.

Smith, A. Pottier, JP Jolivet, F. Babonneau. 'Solid-State 47, 49Ti NMR Determination of the phase Distribution of Titania Nanoparticles5. Chem. Mater., 13, 462 (2001) ' C. Aletru, GN Greaves, G . Sankar. 'Tracking in Deatail the Synthesis of Cadmium Oxide from a Hydroxyl Gel Using Combinations of in Situ X-ray Absorption Fine Structure Spectroscopy, X-ray Diffraction, and Small-Angle X-ray Scattering5. J. Phys. CT^m B., 103, 4147 (1999)) or by the surface plasma resonance effect to estimate the topography changes before and after microwave heating treatment. Referring to FIG. 5, the visible light spectrum transmittance curve of the test piece of the conductive film I before and after the microwave heating treatment is respectively measured, and FIG. 5 shows that the test piece of the conductive film I after microwave heating is used. The light transmittance is remarkably improved. In addition, it can be observed that the surface plasma resonance absorption peak of the gold nanoparticle in the test piece of the conductive film I before the microwave heating is compared with the conventional solution phase gold nanoparticle 520 nm. Surface plasma resonance absorption peaks (HS Zhou, I. Honma, H. Komiyama, 'Controlled synthesis and quantum-size effect in gold-coated nanoparticles5, Phys. Rev. B, 50, 22 201135756 12052 (1994) ' Marie- Christine Daniel, Didier Astruc, sGold Nanoparticles: Assembly, Supramolecular Chemistry,

Quantum-Size-Related Properties, and Applications toward Biology, Catalysis, and Nanotechnology % Chem. Rev., 104, 293 (2004) 'Sujit Kumar Ghosh, Tarasankar Pal,

'Interparticle Coupling Effect on the Surface Plasmon Resonance of Gold Nanoparticles: From Theory to Applications', Chem. Rev., 107, 4797 (2007) ' Vincenzo Amendola and Moreno Meneghetti, 'Size Evaluation of Gold Nanoparticles by UV-vis Spectroscopy5, J Phys. Chem. C 113, 4277 (2009)), the surface plasma absorption peak obtained by measuring the visible light spectrum transmittance of the conductive film test piece i, the peak of which has been red-shifted to 575 nm, should be Chennai The rice particles are adsorbed on the surface of the carbon nanotube wall. After microwave heating treatment, the peaks are obviously blue-shifted and the signal ratio is rapidly decreased. The results show that the gold nanoparticles attached to the wall of the carbon nanotubes may be flattened by melting after microwave heating treatment. The state is coated on the wall of the carbon nanotubes, so it is difficult to maintain the integrity of the nano-particle morphology, and it is also difficult to clearly observe the morphology of the gold nanoparticles when examined by SEM microscopy. The resulting spectrum shows a phenomenon in which the surface electric resonance absorption peak signal is rapidly weakened. Referring again to FIG. 6 and FIG. 7 , respectively, a partially enlarged SEM image of a conductive film of a carbon nanotube composite bonded with gold nanoparticles before and after microwave heat treatment, wherein the brighter portion is adsorbed on the carbon nanotubes. The gold nanoparticle 'cannot observe the actual shape change of the gold nanoparticle on the surface of the carbon nanotube wall', but by comparing the knife barrier of the light 23 201135756 A卩77 in Fig. 6 and Fig. 7 The shape can still be seen that after microwave heating, the gold nanoparticles are transformed from the granulated attachment state into a flat coating on the wall of the carbon nanotube tube and some of the bright parts appear to be incorporated into the nanocarbon. In the case of the tube wall, there may be some molten gold nanoparticles infiltrating into the wall of the carbon nanotube tube, which can further enhance the conductivity of the carbon nanotubes, and also help to improve the composite of the nano-stone The conductive properties of the conductive film made of the object. In addition, the result of the 550 nm transmittance of the conductive film I at the microwave heating is as follows: the sheet resistance before and after the microwave heating treatment, and the microwave transmittance after the microwave heating treatment is 550 nm transmittance 75.07 % 87.91 % sheet resistance 246.7 Ω / □ 152.2 〇 / □

The results show that the microwave heat treatment can synchronously reduce the sheet resistance of the test piece to 38% before untreated, and the light transmittance at 550 nm can be increased by 17%. According to this, it can be clearly confirmed that the metal is combined with the metal. The conductive film of the carboniferous tube composite can improve the electrical conductivity by reducing the contact resistance between the carbon nanotubes by the metal nanoparticles, and can further enhance the penetration of the conductive film by microwave heating treatment. Light rate and conductivity.

&lt;Influence of Microwave Plasma Heating&gt;&lt;Specific Example 2 - Preparation of Carbon Nanotube Composite Conductive Film Bonded with Gold Nanoparticles> Carbon Nanotube Composite Bonded with Gold Nanoparticles The conductive film I was cut into several pieces of 1 cm x 2 cm test piece and subjected to air plasma treatment of (1) 〇 7 t rr for 30 seconds respectively (ii) with an air plasma of 0.7 to rr for 6 sec. Next, the morphology change of the conductive film after the above conditions were observed by an SEM microscope. As shown in Fig. 8 and Fig. 9, the SEM image of 24 201135756 obtained after the conditions (i) and (ii), respectively, can be seen from Fig. 8 by the air plasma action of 〇·7 t〇rr for 3 〇 seconds. After the treatment, the carbon nanotubes which are not completely coated with the gold nanoparticles in the conductive film test piece are etched and vaporized and volatilized in a high-energy plasma environment, and finally a discontinuous linear structure is formed on the surface of the film. As shown in Fig. 9, it is shown that the re-expansion plasma action time is 60 seconds, and after the air plasma of 〇.7 torr is applied, the carbon nanotubes in the conductive film test piece are almost completely etched, and finally left. The densely arranged Chennai: rice particles. Through the foregoing test results, it is shown that the carbon nanotube composite conductive film can easily achieve the result of selective etching in the environment of microwave plasma. Therefore, the nano-carbon tube composite conductive film can be used in the subsequent application to replace the ITO transparent conductive film wet etching process, and the obtained transparent conductive film can be obtained. Relevant application of electronic components, and has great potential for development. In addition, it can be observed from Fig. 9 that the gold nanoparticles coated on the carbon nanotubes are subjected to microwave plasma etching, and the morphology of the gold nanoparticles is approximately spherical, and the gold nanoparticles can still be observed stably. Particles have a tendency to line up along the distribution network of carbon nanotubes, such as the nanopattern with upright carbon nanotubes (Coskun Kocabas, Seong Jun Kang, Taner Ozel, Moonsub Shim, John A. Rogers, ' Improved Synthesis of Aligned Arrays of Single-Walled Carbon Nanotubes and Their Implementation in Thin Film Type Transistors', J. P/z less CTze/w. (7,111, 17879 (2007)) or from linear carbon nanotubes Assembly arrangement (Jun Matsui, Kohei Yamamoto, Nobuhiro Inokuma, Hironori Orikasa, Takashi Kyotania, Tokuji Miyashita, 'Fabrication of densely packed multi-walled 25 201135756 carbon nanotube ultrathin films using a liquid-liquid interface', Μα化r· 17, 3806 (2007)), will have the opportunity to assemble high-density and directional arrays of gold nanoparticle arrays, which can be applied to optical sensors and electrochemical sensors. Development potential. Generally, the sheet resistance of the conductive film can be applied in the range of 10~800Ω/cm2. The sheet resistance of the conductive film used in the general touch panel is 200~800Q/cm2, which is explained by the above results. The sheet resistance value of the conductive film produced by the invention has been in accordance with the application specifications, and has practical application value. It is understood that the method for preparing the conductive film of the carbon nanotube composite with the metal nanoparticle of the present invention can be obtained. The functions and advantages described can achieve the object of the present invention: Since there is only a small contact area between the π m carbonium and the carbon nanotubes, the contact resistance between the carbon tubes is much higher than that of the carbon nanotube film. Electricity becomes the main source of resistance. By attaching a predetermined amount of metal nanoparticles to the carbon nanotubes, an effective high-conductivity channel can be formed at the tube wall to form a contact point, and then combined with microwave post-processing, which can utilize microwave energy quickly. Heating and rapid removal of the heat source (4), under the precondition of avoiding the high temperature (4) substrate sheet 36 from thermal damage, 'promoting adjacent metal nanoparticles to fuse with each other Efficiently enhance the interface between the metal nanoparticle and the carbon nanotube wall=attachment' to further enhance the transmittance and decrease of the conductive film. The method of the present invention can be combined with the metal nanoparticles and the microwave: The way 'to achieve a significant increase in the transmittance and conductivity of conductive films,'. And have the practical value of being able to further improve the performance of the product. 26 201135756 First, hunting by the preparation of carbon nanotube complexes combined with metal nanoparticles to provide a specific ultrasonic frequency to make the carbon nanotube complex solution into atomized particles, and by coating with gas By coating a rotating substrate sheet, a conductive film having a uniform thickness can be obtained, and the performance of the conductive film can be significantly improved by the easy-to-obtain microwave device, showing that the present invention can be easily obtained and a relatively simple process. The carbon nanotube composite conductive film with better light transmittance and conductivity 制 is produced, and the process is simplified to meet the advantages of use and economic benefit. 3. The thickness of the finally obtained conductive film can be controlled by the length of the spin coating to correspondingly produce conductive films of different transmittances and different resistance specifications, so that the manufacturing method of the present invention can be adjusted in a relatively simple control manner. The quality of the products is used in conjunction with different grades of application products. The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are all It is still within the scope of the invention patent. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing a preferred embodiment of a method for fabricating a conductive film of a carbon nanotube composite incorporating a metal nanoparticle of the present invention; FIG. 2 is a schematic view showing the preferred embodiment. The combination of a device used for atomization and spin coating in the embodiment; FIG. 3 is a schematic view showing the state of a microwave device used for microwave post-processing in the preferred embodiment; A schematic diagram showing the change of the rotational speed set at different times when the rotary 汾27 201135756 cloth is arranged in the preferred embodiment; FIG. 5 is a graph showing the conductive film test piece produced by the method of the present invention in microwave heating treatment. Before and after the visible light spectrum transmittance change; Figure ό is a scanning electron microscope photo, illustrating the conductive film test strip prepared by the method of the present invention before the microwave heating treatment; illustrating the variation of the manufacturing method of the present invention; With a carbon nanotube of 0.7 torr

7 is a scanning electron microscope photograph, and the conductive thin film test piece produced by the microwave heat treatment is shown in FIG. 8 as a scanning electron microscope photograph, and the microwave plasma is applied for 30 seconds. The morphology of the conductive film test piece of gold nanoparticles; and the description of the 0.7 t rr of the carbon nanotubes and the gold nai Figure 9 is a scanning electron microscope photo, after microwave plasma treatment for 60 seconds' The morphology of the conductive film of the conductive film is changed.

28 201135756 [Explanation of main component symbols] 30.........Nano-tube composite 39 •...lifting solution 100...•...conductive film 31...atomized particle 4...•...microwave device 32... 41 ••... •...reaction chamber 33.........atomization container 410...•...chamber 34......siphon 42··..·......pumping unit 35...supersonic element 43··.· · •...Supply unit 36... ...substrate sheet 44·····•...transmitting microwave unit Ί 7... C ...... •...name D / 38... Liquid container

29

Claims (1)

201135756 VII. Patent application scope: 1. A method for preparing a conductive thin crucible of a carbon nanotube composite combined with metal nano particles, comprising the following steps: (Ο separately dissolving a predetermined amount of the metal salt compound in an anhydrous organic solvent Prepared as a first solution, and a predetermined amount of carbon nanotubes dissolved in an anhydrous organic solvent to prepare a dispersion, and then the two are mixed and stirred, and then heated to a temperature of 100 〇c at a predetermined heating rate. 16 (rc&amp; maintains a constant temperature for a period of time to form a plurality of carbon nanotube composites combined with a metal nanoparticle; ^ (η) a predetermined amount of carbon nanotube composite is added to a predetermined amount of solvent to prepare a viscosity value between a carbon nanotube composite solution of 1 to 50 c.p; (iii) applying a supersonic atomization frequency to the carbon nanotube composite solution to release the nanocarbon tube composite solution to a plurality of support The atomized particles of the carbon nanotube composites, and provide - carrying gas to make the atomized particles along the shape of the material, the grain control of the atomized particles of the towel, the material is between 0.5 and 50 ° m ; (4) guiding the atomized particles _ placed over the base of the substrate sheet 'by rotating the pedestal' such that the atomized particles uniformly form a carbon nanotube composite conductive film on the surface of the substrate sheet; and (v) The carbon nanotube composite conductive film is placed in a chamber for microwave post-treatment to enhance its light transmittance and electrical conductivity. 2. The metal nanoparticle is combined according to the first claim of the patent scope. The method for preparing a conductive film of a carbon nanotube composite, further comprising a step (4) between the step (4) and the step (7), wherein the step (4) is hot pressing, and the conductive film is disposed at a temperature of 30 201135756. The conductive film is pressed and compacted to a predetermined pressure of the substrate sheet. 3. According to the second item of the patent application, the conductive film of the carbon nanotube composite conductive film combined with the metal nanoparticle is used. And ~ clothing, wherein, in step (4), is applied at a temperature of 5 〇 t ~ 110 ° C τ 2 1 ~ 200 kg / cm 2 pressure hot pressure for 30 seconds ~ 3 〇 minutes. According to the method for preparing a conductive film of a carbon nanotube composite bonded with a metal nanoparticle according to the second aspect of the patent application, in the step (7), the conductive film of the carbon nanotube composite is at a pressure of 25 or more. The microwave heating treatment is carried out in an environment of addition. The method for preparing a conductive film of a carbon nanotube composite bonded with a metal nanoparticle according to the fourth aspect of claim 4, wherein in the step (v), the conductive film of the carbon nanotube composite is subjected to microwave The processing time for processing is less than 3 minutes. The method for preparing a carbon nanotube composite conductive film combined with a metal nanoparticle according to claim 5, wherein in the step (v), when the microwave is post-treated, the chamber is A milk body selected from the group consisting of maintaining a predetermined pressure: &amp; gas, nitrogen, atmosphere, oxygen, hydrogen, and air is provided. 7. The method for producing a conductive film of a non-carbon carbon composite composite incorporating metal nanoparticle according to claim 6, wherein in step (v), the inert gas atmosphere at a pressure greater than 250 ton· The carbon nanotube composite conductive film is subjected to microwave heat treatment to increase the light transmittance of the carbon nanotube composite conductive film and reduce the conductive resistance thereof. 31 201135756 8. The method for preparing a conductive film of a carbon nanotube composite bonded with a metal nanoparticle according to claim 7 of the patent application, further comprising a step (VI) after the step (v) Vi) is a method of performing microwave electrothermal heating treatment on the nano-carboniferous composite 胄 electric thin m by using an a-block formed with a predetermined air-emptive pattern, and first vacuuming the chamber, and then supplying gas to The pressure in the chamber is maintained at Oi t〇rr~2 〇t()n_. 9. The method for producing a conductive film of a carbon nanotube composite bonded with a metal nanoparticle according to claim 8 of the patent application, wherein in the step (vi), the conductive film of the carbon nanotube composite is subjected to The area covered by the 4 cover member directly acts on the microwave plasma, and the portion of the carbon nanotubes in the region which is not adsorbed or coated by the metal nanoparticles is vaporized and volatilized by the action of microwave plasma, and further in the conductive film. The result of selective etching is formed. 10. The method for producing a conductive film of a carbon nanotube composite bonded with a metal nanoparticle according to claim 4, wherein in the step (1), the metal nanoparticles are in the carbon nanotubes The content in the composite is from 1% by weight to 40% by weight. U. The method for preparing a carbon nanotube composite conductive film combined with a metal nanoparticle according to claim 10, wherein in the step (1), the metal on the carbon nanotube composite The nanoparticles are made of a metal selected from the group consisting of tumbling, silver, gold, and the like. 12. The method for preparing a conductive film of a carbon nanotube composite bonded with a metal nanoparticle according to claim 11 of the patent application, in the step (1), forming the nano carbon bonded with the metal nanoparticle After the tube composite, it is filtered first, and washed and dried by an anhydrous organic solvent, 32 201135756 to obtain the carbon nanotube composites. 13. The method for preparing a carbon nanotube composite conductive film incorporating metal nanoparticle according to claim 12, wherein in the step (1), the metal salt compound in the first solution is selected Substances from the group: potassium tetrachloroplatinate, silver nitrate and tetrachloroauric acid. 14. The method for producing a conductive film of a carbon nanotube composite bonded with a metal nanoparticle according to claim 10, wherein in the step (1), the first solution and the dispersion are mixed to form a The first mixture, and • is heated to a loot: ~160 at a predetermined heating rate. (: and after maintaining a constant temperature for a period of time, first cooling to room temperature, and then adding a second solution to the first mixed solution to form - the second mixed liquid '(four) two solution is a predetermined amount of another metal salt compound It is prepared by dissolving in an anhydrous organic solvent. After the second mixture is mixed, the temperature is raised to ι〇〇 at a predetermined heating rate for 6 generations and maintained at a constant temperature--(4), forming a combination of two kinds of metal nanoparticles. a carbon nanotube composite of particles. 15. A method for producing a conductive film of a ruthenium carbon nanotube composite bonded with metal nanoparticles according to the scope of claim U, wherein 'in step (1), the The metal nanoparticles on the carbon nanotube composite include primary nanoparticles and silver nanoparticles, and the weight ratio of the platinum nanoparticles 盥 silver to the 'butyl' silver nanoparticles is 1: 5~1: 20 ° 16. The method for preparing a conductive film of a metal nano-nanocarbon nanotube composite according to the fifteenth aspect of the patent, wherein, in the step: the metal nanoparticles are in the nano carbon f composite Containing 2%, Qiannai particles and silver nanoparticles The weight ratio is substantially 1:10 on 201135756. 17. According to the scope of the patent application, the combination of the metal nano-particles is not the result of the conductive film of the metal-coated nano-particles. In the case of the Ichimachi I method, in the step (1), the metal salt of the first liquid of the 5th sea is compounded with potassium tetrachloroplatinate, and the metal salt compound in the first bath is The upper surface is silver nitrate, and the metal nano particles on the nano carbon two carbon nanoparticles directly bonded to the carbon nanotubes, and the silver nanoparticles bonded to the surface nano particles. The method for producing a conductive thin crucible of a metal (tetra) complex, wherein the first solution, the second solution, and the carbon nanotube dispersion are used in the step (1). The anhydrous organic solvent is anhydrous ethylene glycol. 19. The method for preparing a conductive film of a carbon nanotube composite combined with a metal nanoparticle according to claim 18, wherein in the step (1), the first After a solution is mixed with the carbon nanotube dispersion, it is raised every minute. The rate of ~ is raised to 1 〇〇 t~i6 (rc and maintained at 怔 卜 3 hours. 2 〇. According to the patent scope of claim 18, the carbon nanotube composite conductive film combined with metal nanoparticles The method of the present invention, wherein in the step (1), the second solution is added to the first mixed liquid to form the second mixed liquid, which is increased by 2 per minute. (: ~5 (: rate is raised to 1 〇〇. 〇 〜16〇 it and maintain the strange temperature for 1~3 hours. 21· The method for preparing the conductive film of the carbon nanotube composite combined with the metal nanoparticle according to claim 14 of the patent application, wherein in the step (ii) In the middle, the pure carbon nanotubes of the unbound metal nanoparticles in the pre-twisted ratio are mixed with the carbon nanotubes with the metal/butyl granules of the 2011, 2011, 756, and the squadrons. Adding to the solvent, δ is formulated into a non-meter carbon tube composite solution, and in the step (iii), the atomized particles are simultaneously entrained with the nano-carbon nanotubes. /, anti-official compound and the pure nano-22. According to the scope of the patent application, the method of making the conductive film of the metal-nano-particles Wherein, in step (ii), 'in the carbon nanotube composite solution or the solvent is added - a predetermined amount of the interface agent component, and the surfactant component is used to prevent the nano slaves The complex aggregates. 23. The method according to claim 22, wherein the solvent is a liquid selected from the group consisting of the following groups: : water, ethanol 'isopropyl alcohol and acetone. 24. The method for producing a conductive film of a carbon nanotube composite bonded with a metal nanoparticle according to claim 23, wherein the surfactant group is a substance selected from the group consisting of: an alcohol The sulphate salt 'alkyl sulphate acid salt, α-olefin sulfonate salt, fourth-order ammonium salt, ethylene oxide system, polyoxymethylene sulfonate, and the like. The method for producing a conductive film of a carbon nanotube composite bonded with a metal nanoparticle according to claim 24, wherein the surfactant component is a substance selected from the group consisting of: a straight chain alkyl % acid of c4 to Cl8, a potassium linear alkyl sulfonate of C4 to C18, a sodium sulphate of c4 to C18, a linear alkyl sulphate of C4 to C18, and a C4 to Cl8 Sodium linear alkyl sulfonate, linear alkyl C4~C18 35 201135756 sodium benzene sulfonate, linear C4~C18 丨6, fourth grade C2~Cl6 potassium polyoxyethylene alkyl benzene sulfonate And a linear alkyl benzene sulfate of C4 to C1S, a C2~e salt, an olefin sulfonate, an alkyl group, and the like. The composition of the conductive film of the non-aqueous singular composite in combination with the metal nanoparticle according to claim 25 of the scope of the patent application is selected from the group consisting of sodium dodecyl sulphate. The method for preparing a conductive film of a tube composite combined with a metal nanoparticle according to claim 24 of the patent scope, further comprising - in step (4) and step (8), step (b) is cleaning, Used to remove the surfactant remaining in the conductive film. The method for producing a carbon nanotube composite conductive film combined with metal nanoparticle according to the fourth aspect of the invention, wherein in the step (8), the nano tube compound solution has 1 part by weight a surfactant component, 1 part by weight of a carbon nanotube composite, and a solvent of 1000 to 1 part by weight. 29. A metal nanoparticle according to the scope of claim 28 of the patent application. The method for preparing a conductive film of a particle-free ruthenium complex, wherein, in the step (丨丨丨), the particle diameter of the atomized particles is 2 # m~7 &quot; m. 30. According to the scope of claim 29 The method for preparing a carbon nanotube composite conductive film combined with a metal nanoparticle, wherein the flow rate of the carrier gas in the step (Hi) is from L/min to 200 L/min.