TWI414481B - Combined Preparation of Carbon Nanotube Composite Conductive Films with Metal Nanoparticles - Google Patents
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本發明是有關於一種導電薄膜的製造方法，特別是指一種結合有金屬奈米粒子之奈米碳管複合物導電薄膜的製法。The invention relates to a method for producing a conductive film, in particular to a method for preparing a conductive film of a carbon nanotube composite combined with metal nanoparticles.
隨著液晶螢幕的廣泛應用與發展，透明導電材料的開發一直是熱門的研究主題，應用於顯示器與觸控面板的透明導電薄膜則應具備下列基本特性：(1)在可見光範圍的光透過率與導電率皆高，(2)須能被製為表面平滑的薄膜，且能承受電漿製程環境，(3)容易蝕刻，以形成預定的圖樣(pattern)，(4)可大面積均勻化，(5)低生產成本，(6)無毒並能回收再生。氧化銦錫(indium tin oxide，簡稱為ITO)由於兼具低薄膜片電阻與可見光透光率在80%~90%的特性，已成為透明導電薄膜的最主要原料來源，然而ITO原料中的銦屬於稀有金屬，產量有限，造成供給不穩定及原料成本節節高升，因此，開發新的替代性材料已成為主要的課題。此外，針對近來業界積極投入的觸控式面板與可撓曲面板，由於ITO薄膜不夠柔軟，在使用上相對具有耐用性相對較差與可靠性相對較低的缺點。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 used in displays and touch panels should have the following basic characteristics: (1) Light transmittance in the visible range Both high conductivity and (2) must be made into a smooth surface film and can withstand the plasma process environment, (3) easy to etch to form a predetermined pattern, (4) large area uniformity (5) low production cost, (6) non-toxic and capable of recycling. Indium tin oxide (ITO) has the characteristics of low film resistance and visible light transmittance of 80% to 90%, and has become the most important source of transparent conductive film. However, indium in ITO raw materials. It is a rare metal, and the production is limited, resulting in unstable supply and high 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 have disadvantages in that the ITO film is relatively soft and relatively durable in use and relatively low in reliability.
針對ITO的來源不足與其應用極限等問題，奈米碳管為近來研究開發出來的一種熱門的替代性材料，主要是鑑於奈米碳管材料有許多極優異的光、電、磁與機械特性，且其巨觀物性與化性和材料本身微觀的排列方式與數量有直接關係，而能影響到可應用的產品端，目前並已開發出可投入商業化應用的單壁奈米碳管(single-walled carbon nanotubes，簡稱為SWNT)導電薄膜。In view of the insufficient source of ITO and its application limit, nanocarbon tubes are a popular alternative material developed recently, mainly because of the excellent optical, electrical, magnetic and mechanical properties of nano carbon nanotube materials. Moreover, its macroscopic physical properties and chemical properties are directly related to the microscopic arrangement and quantity of the materials themselves, and can affect the applicable product end. At present, single-walled carbon nanotubes (single) that can be put into commercial application have been developed. -walled carbon nanotubes (referred to as SWNT) conductive film.
單壁式奈米碳管導電薄膜主要是採用濾膜法與噴灑法製成。其中，濾膜法是先以雷射法合成SWNT，並以高濃度的硝酸溶液酸洗後，將其加入含有特定界面活性劑的溶劑中形成奈米碳管溶液，再以特定的濾紙過濾使該等奈米碳管停駐於濾紙表面形成奈米碳管濾膜，接著，將該奈米碳管濾膜轉貼至透明基板上，再利用丙酮除去濾紙部分，只留下奈米碳管，就能製得單壁式奈米碳管導電薄膜(“Transparent,Conductive Carbon Nanotube Films”,Z.Wu etc.,Science 2004 ,305,1273、”Effect of SOCl2 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 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 ("Transparent, Conductive Carbon Nanotube Films", Z. Wu et., Science 2004 , 305, 1273, "Effect of SOCl2 Treatment on Electrical and Mechanical Properties of Single-Wall" Carbon Nanotube Networks", U. Dettlaff-Weglikowska et . , J. Am. Chem. Soc. , 2005, 127, 5125-5131).
以噴灑法製備單壁式奈米碳管導電薄膜的製法則是將預定量的單壁式奈米碳管加入並使其分散於含有特定界面活性劑的溶劑中形成奈米碳管溶液，將該奈米碳管溶液離心後，取溶液上層50%的部分噴灑於表面溫度維持在100℃的聚對苯二甲酸乙二酯(poly(ethylene terephthalate)，簡稱為PET)基材上，接著，以去離子水清洗並烘乾，就能製得單壁式奈米碳管導電薄膜(“Effect of Acid Treatment on Carbon Nanotube-Based Flexible Transparent Conducting Films”,J. Am. Chem. Soc. ,2007,129,7758-7759)。The method for preparing a single-walled carbon nanotube conductive film by spraying method is to add a predetermined amount of single-walled carbon nanotubes and disperse it in a solvent containing a specific surfactant to form a carbon nanotube solution, which will After centrifugation of the carbon nanotube solution, a 50% portion of the upper layer of the solution is sprayed onto a poly(ethylene terephthalate, abbreviated as PET) substrate having a surface temperature maintained at 100 ° C. A single-walled carbon nanotube conductive film ("Effect of Acid Treatment on Carbon Nanotube-Based Flexible Transparent Conducting Films", J. Am. Chem. Soc. , 2007, can be obtained by washing and drying with deionized water . 129, 7758-7759).
此外，雖然奈米碳管本身已具有優異的光電特性，但奈米碳管間的接觸電阻仍為單根奈米碳管電阻的103 倍，因此，上述單壁式奈米碳管導電薄膜在奈米碳管間的接觸電阻仍是提高導電薄膜之導電性的研究重點。In addition, although the carbon nanotubes themselves have excellent photoelectric characteristics, the contact resistance between the carbon nanotubes is still 10 3 times that of the single carbon nanotubes. Therefore, the above-mentioned single-walled carbon nanotube conductive film Contact resistance between carbon nanotubes is still the focus of research to improve the conductivity of conductive films.
雖然學界與業界的積極研究開發，已發展出各種互有優劣的透明導電薄膜，而且其中的單壁式奈米碳管導電薄膜的製造技術也進入準備商業化的階段，並有可取代ITO薄膜的趨勢，但相關配套的製程技術並非短時間就能成功，為因應未來需求，並創造出更多更人性化的人機介面產品及軟性電子產品，有關觸控面板、可撓曲面板、透明電極等液晶顯示器的製程技術也將有所變革，其中，材料技術的成熟度將是關鍵的要素，因此，仍有持續開發不同類型的材料技術與改善現有材料性能的需求，以提供更多元的選擇與應用，進而提升產品使用性能，及降低生產成本與發展出更精進的製程技術。Although the academic and industry's active research and development, has developed a variety of transparent conductive films, and the manufacturing technology of single-walled carbon nanotube conductive film has also entered the stage of commercialization, and can replace the ITO film. Trends, but the related process technology will not be successful in a short period of time, in response to future needs, and create more humane interface products and soft electronic products, related to touch panels, flexible panels, transparent The process technology of liquid crystal displays such as 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 to provide more elements. The choice and application, thereby improving product performance, reducing production costs and developing more advanced process technology.
因此，本發明的目的，是在提供一種製程較簡化且能進一步提升導電性能的結合有金屬奈米粒子之奈米碳管複合物導電薄膜的製法。SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for producing a carbon nanotube composite conductive film incorporating metal nanoparticles in which the process is simplified and the conductivity can be further improved.
於是，本發明結合有金屬奈米粒子之奈米碳管複合物導電薄膜的製法，包含下列步驟：Therefore, the method for preparing a carbon nanotube composite conductive film incorporating metal nano particles comprises the following steps:
(i) 分別將一預定量之金屬鹽化合物溶於一無水有機溶劑中配製為一第一溶液，及將一預定量之奈米碳管溶於一無水有機溶劑中配製為一分散液，再將二者混合攪拌後，以預定的升溫速率升溫至100℃~160℃並維持恆溫一段時間，以形成多數個結合有金屬奈米粒子的奈米碳管複合物；(i) separately dissolving a predetermined amount of the metal salt compound in an anhydrous organic solvent to prepare a first solution, and dissolving a predetermined amount of the carbon nanotubes in an anhydrous organic solvent to prepare a dispersion, and then After mixing and stirring the two, the temperature is raised to 100 ° C ~ 160 ° C at a predetermined heating rate and maintained at a constant temperature for a period of time to form a plurality of carbon nanotube composites combined with metal nanoparticles;
(ii)將預定量的奈米碳管複合物加入一預定量的溶劑中調配成黏度值介於1~50c.p的奈米碳管複合物溶液；(ii) adding a predetermined amount of the carbon nanotube composite to a predetermined amount of solvent to prepare a carbon nanotube composite solution having a viscosity of 1 to 50 c.p;
(iii)施加一超音波霧化頻率於該奈米碳管複合物溶液，使該奈米碳管複合物溶液釋放出多數個挾帶有該等奈米碳管複合物的霧化顆粒，並提供一攜帶氣體使該等霧化顆粒沿一預定路徑傳送，其中，該等霧化顆粒的粒徑是介於0.5μm~50μm；及(iii) applying an ultrasonic atomization frequency to the carbon nanotube composite solution, causing the carbon nanotube complex solution to release a plurality of atomized particles having the carbon nanotube complexes, and Providing a carrier gas for transporting the atomized particles along a predetermined path, wherein the atomized particles have a particle diameter of between 0.5 μm and 50 μm;
(iv)將該等霧化顆粒引導至一放置有一基材片的基座上方，藉由旋轉該基座，使該等霧化顆粒於該基材片表面均勻地形成一奈米碳管複合物導電薄膜。(iv) directing the atomized particles onto a susceptor on which a substrate sheet is placed, and by rotating the susceptor, the atomized particles are uniformly formed on the surface of the substrate sheet to form a carbon nanotube composite Conductive film.
本發明的有益效果在於：以奈米碳管配合金屬鹽化合物製備結合有金屬奈米粒子的奈米碳管複合物，據此製造出的導電薄膜產品能表現較佳導電性能，此外，透過施加超音波使該奈米碳管複合物溶液形成霧化顆粒，有利於該等奈米碳管複合物被分散帶出，再配合旋轉塗佈方式，使該等奈米碳管能夠在該基材片表面均勻地形成導電薄膜，還使本發明具有製程技術與使用設備相對較簡便，而能有效節省製造成本的優點。The invention has the beneficial effects that the carbon nanotube composite combined with the metal nanoparticle is prepared by using a carbon nanotube compound and a metal salt compound, and the conductive film product produced thereby can exhibit better conductivity and, in addition, through application The ultrasonic wave causes the carbon nanotube composite solution to form atomized particles, which facilitates the dispersion of the carbon nanotube composites, and is combined with a spin coating method to enable the carbon nanotubes to be on the substrate. The surface of the sheet uniformly forms a conductive film, and the invention has the advantages of relatively simple process technology and equipment, and can effectively save manufacturing cost.
有關本發明之前述及其他技術內容、特點與功效，在以下配合參考圖式之一個較佳實施例的詳細說明中，將可清楚的呈現。The above and other technical contents, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments.
參閱圖1與圖2，本發明結合有金屬奈米粒子之奈米碳管複合物導電薄膜的製法的一較佳實施例包含下列步驟：步驟101是分別將一預定量之金屬鹽化合物溶於一無水乙二醇中配製為一第一溶液，及將一預定量之奈米碳管溶於一無水乙二醇中配製為一分散液，再將二者混合攪拌後，以每分鐘上升2℃~5℃的升溫速率升溫至100℃~160℃並維持恆溫1~3小時，使金屬鹽化合物中的金屬離子被還原為金屬奈米粒子並附著於該等奈米碳管上，以形成多數個結合有金屬奈米粒子的奈米碳管複合物後，直接趁熱過濾，並以無水乙醇沖洗數次，及於溫度80℃下進行真空乾燥處理，就能獲得該等奈米碳管複合物。該奈米碳管可為多層壁奈米碳管(multi-walled nanotubes，簡稱為MWNT)或單壁奈米碳管(single-walled carbon nanotubes，簡稱為SWNT)，在本實施例是使用多層壁奈米碳管。Referring to FIG. 1 and FIG. 2, a preferred embodiment of the method for fabricating a carbon nanotube composite conductive film incorporating metal nanoparticles comprises the following steps: Step 101 is to dissolve a predetermined amount of a metal salt compound, respectively. Preparing a first solution in an anhydrous ethylene glycol, and dissolving a predetermined amount of carbon nanotubes in an anhydrous ethylene glycol to prepare a dispersion, and then mixing and stirring the mixture to increase by 2 per minute. The temperature rise rate of °C~5°C is raised to 100°C~160°C and maintained at a constant temperature for 1-3 hours, so that the metal ions in the metal salt compound are reduced to metal nanoparticles and adhered to the carbon nanotubes to form After a plurality of carbon nanotube composites combined with metal nanoparticles, they are directly filtered while hot, washed several times with absolute ethanol, and vacuum dried at a temperature of 80 ° C to obtain the carbon nanotubes. Complex. The carbon nanotubes may be multi-walled nanotubes (MWNTs) or single-walled carbon nanotubes (SWNTs). In this embodiment, multi-walled walls are used. Carbon nanotubes.
值得說明的是，在此步驟主要的控制參數為反應溫度與升溫速率，而在此使用乙二醇為溶劑的主要的特色為：(1)乙二醇本身為黏度較高的溶劑系統，其高極性特徵有助於溶解少量的金屬鹽化合物，且其高黏度可防止金屬離子擴散，藉由升溫控制其黏稠度與金屬離子的擴散速率，可影響所生成的金屬奈米粒子懸浮於乙二醇中或是附著於奈米碳管管壁的比率。(2)由於乙二醇的沸點為198℃，使該第一溶液與分散液混合後可升溫至較高溫度而有助於使活性較高的金屬離子還原為零價的金屬原子，例如，鉑離子要在120℃才能達到高還原比率，而銀離子需高達150℃才能達到相同的效果。(3)乙二醇氧化後所生成的乙二酸也是良好的金屬奈米粒子保護基，對於金屬奈米粒子的粒徑控制與金屬奈米粒子未結合於奈米碳管前的穩定性有重要作用。但是，乙二酸的熱分解溫度為175℃。因此，為有效發揮乙二醇、乙二酸降低金屬奈米粒子聚集與裸露懸浮的比例，其反應溫度應低於175℃，且應高於100℃以利於金屬離子進行還原，因此，在此步驟將升溫的最終反應溫度限制在100℃~160℃。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) Ethylene glycol itself is a solvent system with high viscosity, The high polarity feature helps to dissolve a small amount of metal salt compounds, and its high viscosity prevents metal ions from diffusing. By controlling the viscosity and the diffusion rate of metal ions by temperature rise, the generated metal nanoparticles can be suspended in Ethylene. The ratio of alcohol to the wall of the carbon nanotube tube. (2) Since the boiling point of ethylene glycol is 198 ° C, the first solution and the dispersion may be heated to a higher temperature to help lower 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, while silver ions need to be as high as 150 ° C to achieve the same effect. (3) The oxalic acid formed after the oxidation of ethylene glycol is also a good metal nanoparticle protection group. For the particle size control of the metal nanoparticle and the stability of the metal nanoparticle before it is bonded to the carbon nanotube Important role. However, the thermal decomposition temperature of oxalic acid is 175 °C. Therefore, in order to effectively exert the ratio of ethylene glycol and oxalic acid to reduce the aggregation of metal nanoparticles and bare suspension, the reaction temperature should be lower than 175 ° C, and should be higher than 100 ° C to facilitate the reduction of metal ions, therefore, here The step limits the final reaction temperature for the temperature rise to 100 ° C to 160 ° C.
另外，升溫速率則是與所形成的金屬奈米粒子的粒徑與相較於原始所添加的金屬離子量附著於奈米碳管的金屬奈米粒子比例有關，升溫速率越快，則所形成的金屬奈米粒子的粒徑越小，且附著到該等奈米碳管的比例也較低。以製備結合有鉑與銀奈米粒子之奈米碳管複合物為例，是分別將每分鐘上升2℃定義為緩慢升溫，及將每分鐘上升5℃定義為快速升溫。且以2℃/分鐘的升溫速率所製得的結合有金屬奈米粒子的奈米碳管複合物，經穿透式電子顯微鏡觀察顯示奈米碳管管壁上附著的金屬奈米粒子較密集，且該等金屬奈米粒子的平均粒徑為3.84nm，其實際粒徑分布範圍為2nm~7nm，經900℃鍛燒所獲得熱分析結果可知，其金屬負載率為原始金屬添加量的99%，充分顯示高比率的金屬負載。而以5℃/分鐘的升溫速率所製得的結合有金屬奈米粒子的奈米碳管複合物，經穿透式電子顯微鏡觀察顯示奈米碳管管壁上附著的金屬奈米粒子密度略低於2℃/分鐘者，且其金屬奈米粒子的平均粒徑降低至3.00nm，其實際粒徑分布範圍放大至1nm~7nm，而經900℃鍛燒所獲得熱分析結果顯示，其金屬負載率僅為原始金屬添加量的89%。因此，在升溫速率的選擇上，需配合後續應用方向，當以催化或導電性為主要應用方向時，則選用金屬奈米粒子附著比例較高的緩慢升溫速率，當以透光率或小粒徑為主要考量時，則以較快的升溫速率為選擇條件。In addition, the heating rate is related to the particle diameter of the formed metal nanoparticles and the ratio of the metal nanoparticles to which the amount of the metal ions originally added is attached to the carbon nanotubes, and the faster the rate of temperature rise, the formation The smaller the particle size of the metal nanoparticles, the lower the ratio of adhesion to the carbon nanotubes. For the preparation of a carbon nanotube composite in which platinum and silver nanoparticles are combined, an increase of 2 ° C per minute is defined as a slow temperature rise, and a rise of 5 ° C per minute is defined as a rapid temperature rise. The carbon nanotube composites with metal nanoparticles prepared at a heating rate of 2 ° C / min were observed by transmission electron microscopy to show that the metal nanoparticles attached to the walls of the carbon nanotubes were dense. The average particle diameter of the metal nanoparticles is 3.84 nm, and the actual particle size distribution ranges from 2 nm to 7 nm. The thermal analysis results obtained by calcination at 900 ° C show that the metal loading rate is 99 of the original metal addition amount. %, fully showing a high ratio of metal load. The carbon nanotube composites with metal nanoparticles prepared at a heating rate of 5 ° C / min were observed by a transmission electron microscope to show the density of metal nanoparticles attached to the wall of the carbon nanotubes. Below 2 ° C / min, and the average particle size of the metal nanoparticles is reduced to 3.00 nm, the actual particle size distribution range is enlarged to 1 nm ~ 7 nm, and the thermal analysis obtained by calcination at 900 ° C shows that the metal The load rate is 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 nanoparticle adhesion ratio is selected, when the transmittance or the small particle is used. When the diameter is the main consideration, the faster heating rate is selected as the selection condition.
其中，該等奈米碳管複合物上的該等金屬奈米粒子為一選自下列群組中的金屬所製成：鉑、銀、金，及其等的組合。且該第一溶液的金屬鹽化合物為一選自下列群組中的物質：四氯鉑酸鉀(K2 PtCl4 )、硝酸銀(AgNO3 )及四氯金酸(HAuCl4 )。藉由使用不同的金屬鹽化合物，可形成結合有不同金屬奈米粒子的奈米碳管複合物，並能透過調整金屬鹽化合物與奈米碳管的用量比例控制該等奈米碳管複合物中的金屬奈米粒子的含量。該等金屬奈米粒子在該等奈米碳管複合物中的含量較佳為10wt%~40wt%。Wherein, the metal nanoparticles on the carbon nanotube composite are made of a metal selected from the group consisting of platinum, silver, gold, and the like. And the metal salt compound of the first solution is a substance selected from the group consisting of potassium tetrachloroplatinate (K 2 PtCl 4 ), silver nitrate (AgNO 3 ), and tetrachloroauric acid (HAuCl 4 ). 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. The content of metal nanoparticles in the medium. The content of the metal nanoparticles in the carbon nanotube composites is preferably from 10% by weight to 40% by weight.
當該等奈米碳管複合物上只具有一種金屬奈米粒子時，是如前所述地，將第一溶液與該分散液混合形成的一第一混合液於升溫至100℃~160℃並維持恆溫一段時間後，直接趁熱過濾，就能使金屬鹽化合物中的金屬離子被還原並分別結合於該等碳米碳管上，進而形成具有一種金屬奈米粒子的奈米碳管複合物。When the carbon nanotube composite has only one type of metal nanoparticle, as described above, a first mixture formed by mixing the first solution and the dispersion is heated to 100 ° C to 160 ° C. After maintaining a constant temperature for a period of time, direct thermal filtration can reduce the metal ions in the metal salt compound and bond them to the carbon nanotubes, thereby forming a carbon nanotube composite having a metal nanoparticle. Things.
此外，該等奈米碳管複合物上也可以具有二種以上的金屬奈米粒子，例如，當該等奈米碳管複合物上具有鉑與銀二種金屬奈米粒子時，其製備方法是將預定量的四氯鉑酸鉀溶於無水乙二醇中配製為該第一溶液，再與含有奈米碳管的分散液相混合形成該第一混合液，且以每分鐘上升2℃~5℃的速率升溫至100℃~160℃並維持恆溫1~3小時後，可使鉑離子被還原為鉑奈米粒子並分別結合於該等奈米碳管上，此時，先冷卻至室溫，再於該第一混合液中加入一第二溶液而形成一第二混合液，該第二溶液是由預定量的硝酸銀溶於無水乙二醇中配製而成，該第二混合液經攪拌後，以每分鐘上升2℃~5℃的升溫速率升溫至100℃~160℃並維持恆溫一段時間後，使硝酸銀中的銀離子被還原為銀奈米粒子並分別結合於該等鉑奈米粒子上，以形成結合有鉑與銀二種金屬奈米粒子的奈米碳管複合物。由於銀奈米粒子與奈米碳管管壁間的附著性不如鉑奈米粒子的附著性強，而鉑的原料價格接近銀的100倍，為了增加奈米碳管複合物在導電性產品的商業化實用價值，先以少量的鉑奈米粒子結合於奈米碳管，再透過該等鉑奈米粒子使該等銀奈米粒子間接結合於奈米碳管上，因此，藉由使用二種金屬奈米粒子，可以達到使金屬奈米子附著於奈米碳管的預定效果，同時還能降低原料成本。其中，鉑奈米粒子與銀奈米粒子的重量比較佳為1：5~1：20。若考量原料成本與附著效果的平衡，則更佳為1：10，且該等鉑奈米粒子與銀奈米粒子在該奈米碳管複合物中的含量較佳為20wt%，在此條件下可得到最佳的負載效率(即金屬總附著率，以附著於奈米碳管的金屬奈米粒子重量與金屬鹽化合物中金屬離子重量的比值表示)。In addition, the carbon nanotube composites may have two or more kinds of metal nanoparticles. For example, when the carbon nanotube composites have platinum and silver metal nanoparticles, the preparation method is Dissolving a predetermined amount of potassium tetrachloroplatinate in anhydrous ethylene glycol to prepare the first solution, and then mixing with a dispersed liquid phase containing a carbon nanotube to form the first mixed liquid, and rising by 2 ° C per minute~ After the temperature is raised to 100 ° C to 160 ° C at a rate of 5 ° C and maintained at a constant temperature for 1 to 3 hours, the platinum ions can be reduced to platinum nanoparticles and respectively bonded to the carbon nanotubes. At this time, the chamber is cooled first. Warming, adding a second solution to the first mixture to form a second mixture, the second solution is prepared by dissolving a predetermined amount of silver nitrate in anhydrous ethylene glycol, and the second mixture is prepared by After stirring, the temperature is raised to 100 ° C ~ 160 ° C at a temperature increase rate of 2 ° C ~ 5 ° C per minute and maintained at a constant temperature for a period of time, then the silver ions in the silver nitrate are reduced to silver nanoparticles and respectively bonded to the platinum On the rice particles to form a naphthalene containing two kinds of metal nanoparticles, platinum and silver. Carbon nanotube composite. Since the adhesion between the silver nanoparticle and the wall of the carbon nanotube is not as strong as that of the platinum nanoparticle, and the raw material price of platinum is close to 100 times that of the silver, in order to increase the carbon nanotube composite in the conductive product Commercially useful value, firstly bound to the carbon nanotubes with a small amount of platinum nanoparticles, and then the silver nanoparticles are indirectly bonded to the carbon nanotubes through the platinum nanoparticles, therefore, by using two The metal nanoparticle can achieve the predetermined effect of attaching the metal nanoparticle to the carbon nanotube, and at the same time reduce the raw material cost. Among them, the weight of the platinum nanoparticle and the silver nanoparticle is preferably 1:5 to 1:20. If the balance between the raw material cost and the adhesion effect is considered, it is more preferably 1:10, and the content of the platinum nanoparticle and the silver nanoparticle in the carbon nanotube composite is preferably 20% by weight. The optimum loading efficiency (i.e., 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.
步驟102是配製一奈米碳管複合物溶液30，將1重量份的奈米碳管複合物及1重量份的界面活性劑組份分別加入1000~1000000重量份的溶劑中調配成黏度值介於1~50c.p的奈米碳管複合物溶液30，上述黏度值是在室溫下量測之值。Step 102 is to prepare a carbon nanotube composite solution 30, and add 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 the solvent respectively to prepare a viscosity value. In the carbon nanotube composite solution 30 of 1 to 50 c.p, the above viscosity value is a value measured at room temperature.
該界面活性劑組份是用以防止該等奈米碳管複合物聚集，且為一選自下列群組中的物質：醇之硫酸酯鹽(sulfated alcohol，通式為ROSO3 - M+ )、烷基磺酸鹽(alkylsulfonate，通式為RSO3 - M+ )、α-烯烴磺酸鹽(alpha-olefinsulphonate，簡稱為AOS，通式為RCH=CH(CH2 )n -SO3 M)、第四級銨鹽(Quaternary ammonium salt，通式為)、環氧乙烷系(亦稱聚乙二醇系，polyoxyethylene，簡稱為POE)、聚氧乙烯烷基醚(又稱為脂肪醇聚氧乙烯醚、醚醇，alcohol ethoxylate，簡稱為AE，通式為RO(CH2 CH2 O)n H)，及其等之組合。The surfactant component is for preventing the aggregation of the carbon nanotube composites, and is a substance selected from the group consisting of a sulfated alcohol (ROSO 3 - M + ) , alkylsulfonate (formula RSO 3 - M + ), α-olefin sulfonate (alpha-olefinsulphonate, abbreviated as AOS, of the formula RCH=CH(CH 2 ) n -SO 3 M) Quaternary ammonium salt ), ethylene oxide (also known as polyethylene glycol, polyoxyethylene, POE for short), polyoxyethylene alkyl ether (also known as fatty alcohol polyoxyethylene ether, ether alcohol, alcohol ethoxylate, referred to as AE, The formula is RO(CH 2 CH 2 O) n H), and combinations thereof.
較佳地，該界面活性劑為一選自下列群組中的物質：C4 ~C18 之直鏈烷基磺酸鈉(通式為RSO3 - Na+ )、C4 ~C18 之直鏈烷基磺酸鉀(通式為RSO3 - K+ )、C4 ~C18 之直鏈烷基硫酸鈉(通式為ROSO3 - Na+ )、C4 ~C18 之直鏈烷基硫酸鉀(通式為ROSO3 - K+ )、C4 ~C18 之直鏈烷基苯磺酸鈉(通式為RC6 H4 SO3 - Na+ )、C4 ~C18 之直鏈烷基苯磺酸鉀(通式為RC6 H4 SO3 - K+ )、C4 ~C18 之直鏈烷基苯硫酸鈉(通式為ROC6 H4 SO3 - Na+ )、C4 ~C18 之直鏈烷基苯硫酸鉀(通式為ROC6 H4 SO3 - K+ )、C2 ~C16 之直鏈烷基四級銨鹽、α-烯烴磺酸鹽(簡稱為AOS，通式為RCH=CH(CH2 )n -SO3 M，其中，n=14~16，且M為鹼金族離子)、烷基為C2 ~C16 之聚氧乙烯烷基醚(簡稱為AE，通式為RO(CH2 CH2 O)n H，n=5~30)，及其等之組合。藉此，可達到較佳的分散效果，在本實施例中，是選用十二烷基磺酸鈉(sodium dodecyl sulfate，簡稱為SDS)作為該界面活性劑。Preferably, the surfactant is a substance selected from the group consisting of sodium C 4 ~ C 18 linear alkyl sulfonate (formula RSO 3 - Na + ), C 4 ~ C 18 straight Potassium alkane sulfonate (formula RSO 3 - K + ), linear alkyl sodium sulfate of C 4 ~ C 18 (formula of ROSO 3 - Na + ), linear alkyl group of C 4 ~ C 18 Potassium sulfate (formula of ROSO 3 - K + ), sodium C 4 ~ C 18 linear alkylbenzene sulfonate (formula RC 6 H 4 SO 3 - Na + ), linear chain of C 4 ~ C 18 Potassium alkylbenzene sulfonate (formula RC 6 H 4 SO 3 - K + ), linear C 4 -C 18 linear alkyl benzene sulphate (formula: ROC 6 H 4 SO 3 - Na + ), C 4 to C 18 linear alkyl benzene sulfate (formula: ROC 6 H 4 SO 3 - K + ), C 2 to C 16 linear alkyl quaternary ammonium salt, α-olefin sulfonate (abbreviation is the AOS, the formula RCH = CH (CH 2) n -SO 3 M, where, n = 14 ~ 16, and M is an alkali metal ion group), alkyl polyoxyethylene alkyl is a C 2 ~ C 16 of Ether (abbreviated as AE, the formula is RO(CH 2 CH 2 O) n H, n=5~30), and combinations thereof. Thereby, a better dispersion effect can be achieved. In the present embodiment, sodium dodecyl sulfate (SDS) is selected as the surfactant.
其中，該溶劑為一選自下列群組中的液體：水、乙醇、異丙醇及丙酮，在本實施例中，是以水為溶劑。配製時，於溶劑中添加該等奈米碳管複合物與該界面活性劑後，可先以功率750W的探頭式超音波震盪分散器(機型：Sonics & Materials,Inc.「SONICSVCX750」)對該奈米碳管複合物溶液30以20%功率作用5分鐘，及30%功率作用5分鐘，以防止該等奈米碳管複合物聚集並呈均勻分散的狀態。Wherein the solvent is a liquid selected from the group consisting of water, ethanol, isopropanol and acetone, and in the present embodiment, water is used as a solvent. When preparing, adding the carbon nanotube complex and the surfactant to the solvent, the probe type ultrasonic shock diffuser with power of 750W can be used first (model: Sonics & Materials, Inc. "SONICS The VCX 750") was applied to the carbon nanotube composite solution 30 at 20% power for 5 minutes and at 30% power for 5 minutes to prevent the carbon nanotube composites from aggregating and uniformly dispersed.
步驟103是施加一超音波霧化頻率於該奈米碳管複合物溶液30，使該奈米碳管複合物溶液30霧化，上述的霧化是指該奈米碳管複合物溶液30會釋放出多數個挾帶有該等奈米碳管複合物的霧化顆粒31，並提供一攜帶氣體32使該等霧化顆粒31沿一預定路徑傳送。其中，該奈米碳管複合物溶液30是盛裝於一霧化容器33中，且該溶液30的液面是藉由一虹吸管34維持在固定高度，藉此，使產生該超音波頻率的超音波元件35恆位於液面下固定深度處，以控制該溶液液面所承受的能量固定，及所產生的霧化顆粒31的粒徑能維持一致。其中，該虹吸管34是連接在該霧化容器33與一貯液容器38之間，該貯液容器38是置於一升降座39上，以受其連動而上下位移，並能藉此控制該霧化容器33中的液面高度。較佳地，為了使流到該貯液容器38的奈米碳管複合物溶液30中的奈米碳管複合物仍然能維持分散狀態，通常會在該貯液溶器38中再加裝一探頭式超音波震盪分散器(圖未示)持續對回流到該貯液容器38的溶液作用。Step 103 is to apply an ultrasonic atomization frequency to the carbon nanotube composite solution 30 to atomize the carbon nanotube composite solution 30. The atomization refers to the carbon nanotube composite solution 30. A plurality of atomized particles 31 with such carbon nanotube composites are released and a carrier gas 32 is provided to transport the atomized particles 31 along a predetermined path. Wherein, the carbon nanotube composite solution 30 is contained in an atomization container 33, and the liquid level of the solution 30 is maintained at a fixed height by a siphon tube 34, thereby generating the supersonic frequency super The acoustic wave element 35 is constantly located at a fixed depth below the liquid surface to control the fixation of the energy received by the liquid level of the solution, and the particle size of the generated atomized particles 31 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 seat 39 to be vertically displaced by the linkage thereof, and can thereby control the The liquid level in the atomizing container 33. 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 38, an additional one is usually added to the liquid storage device 38. A probe-type ultrasonic oscillating disperser (not shown) continues to act on the solution that is returned to the reservoir 38.
在本實施例中則是採用1.65MHz的超音波霧化頻率(在本實施例中所用的超音波霧化器的機型為：普崴電子Pro-Wave Electronic Corp M165D25、M165D20)，而該等霧化顆粒31的粒徑則是介於0.5μm~50μm，且較佳是介於2μm~7μm，在本實施例中，則是配合超音波霧化頻率使該等霧化顆粒31的粒徑實質上維持在3μm左右。In the present embodiment, the ultrasonic atomization frequency of 1.65 MHz is used (the ultrasonic atomizer used in this embodiment is: Pro-Wave Electronic Corp M165D25, M165D20), and these The particle size of the atomized particles 31 is between 0.5 μm and 50 μm, and preferably between 2 μm and 7 μm. In the present embodiment, the particle size of the atomized particles 31 is matched with the ultrasonic atomization frequency. It is maintained at approximately 3 μm.
為了符合所要求的粒徑大小，可透過下列公式推算該超音波的頻率範圍，以較快速地調整到所要求的霧化顆粒31尺寸：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:
其中，D為霧化顆粒的粒徑，T為表面張力係數(N/cm)，ρ為溶液密度(g/cm3 )，f為超音波霧化頻率(Hz)，及α為0.34的常數值。(Ultrasonics Volume 22,Issue 6,November 1984,Pages 259-260)Where D is the particle size of the atomized particles, T is the surface tension coefficient (N/cm), ρ is the solution density (g/cm 3 ), f is the ultrasonic atomization frequency (Hz), and α is 0.34. Value. (Ultrasonics Volume 22, Issue 6, November 1984, Pages 259-260)
較佳地，該攜帶氣體32的流速為1L/min~200L/min，在本實施例中，該攜帶氣體32的流速則是設定為22L/min，且該攜帶氣體32為氮氣。Preferably, the flow rate of the carrier gas 32 is from 1 L/min to 200 L/min. In the present embodiment, the flow rate of the carrier gas 32 is set to 22 L/min, and the carrier gas 32 is nitrogen.
步驟104是旋轉塗佈，將該等霧化顆粒31引導至一放置有一基材片36的基座37上方，藉由旋轉該基座37，使該等霧化顆粒31於該基材片36表面，均勻地形成一導電薄膜。Step 104 is spin coating, and the atomized particles 31 are guided onto a susceptor 37 on which a substrate sheet 36 is placed. By rotating the susceptor 37, the atomized particles 31 are placed on the substrate sheet 36. The surface uniformly forms a conductive film.
進行旋轉途佈時，該基座37是先經一次濕潤旋轉塗佈與一次初步成膜旋轉塗佈的預處理，再重複進行多次周期性的再成膜旋轉塗佈，且在該再成膜旋轉塗佈中是依序經由一低速轉速、一中速轉速及一高速轉速的周期變換旋轉。在本實施例中，該低速轉速較佳為300~450r.p.m.，該中速轉速較佳是控制在450~900r.p.m.，及該高速轉速較佳是1200~6000r.p.m.。其中，進行濕潤旋轉塗佈的轉速為300r.p.m與450r.p.m.相交替數次，進行初步成膜旋轉塗佈的轉速則為自450r.p.m.依階梯式上升到6000r.p.m.後，再進入周期性的再成膜旋轉。When the rotating cloth is rotated, the susceptor 37 is pre-treated by one wet spin coating and one preliminary film spin coating, and then repeated periodic re-filming spin coating is repeated, and the repulsion is repeated. In the film spin coating, the rotation is sequentially changed through a cycle of a low speed, a medium speed, and a high speed. In this embodiment, the low speed is preferably 300 to 450 r.p.m., and the medium speed is preferably controlled at 450 to 900 r.p.m., and the high speed is preferably 1200 to 6000 r.p.m. Among them, the rotational speed of the wet spin coating is 300r.pm and 450r.pm alternately, and the rotational speed of the preliminary film spin coating is from 450r.pm to 6000r.pm, and then enters the cycle. Sexual re-filming rotation.
步驟105是熱壓，是於預定溫度下對設置有該導電薄膜的基材片36施加預定壓力，用以使該導電薄膜被壓密緊實並形成較緻密穩定的結構，及使該等奈米碳管複合物之間形成較緊密的連結，而有助於降低該導電薄膜的表面電阻，使該導電薄膜能夠表現更佳的導電度。Step 105 is hot pressing, applying a predetermined pressure to the substrate sheet 36 provided with the conductive film at a predetermined temperature, so that the conductive film is compacted and compacted to form a denser and stable structure, and the A tight junction is formed between the carbon nanotube composites to help reduce the surface resistance of the conductive film, so that the conductive film can exhibit better conductivity.
較佳地，進行熱壓時是於溫度50℃~110℃下施加1~200kg/cm2 的壓力熱壓30秒~30分鐘，在本實施例中則是在溫度70℃下，施加100kg/cm2 的壓力進行熱壓30分鐘，但不應以此限制熱壓時間，通常熱壓越久，導電性會越佳，但熱壓超過30分鐘後導電性的提升反而不顯著，所以熱壓時間宜控制在30分鐘以內。Preferably, when hot pressing is performed, a pressure of 1 to 200 kg/cm 2 is applied at a temperature of 50 ° C to 110 ° C for 30 seconds to 30 minutes, and in the present embodiment, 100 kg / is applied at a temperature of 70 ° C. The pressure of cm 2 is hot pressed for 30 minutes, but this should not limit the hot pressing time. Generally, the longer the hot pressing, the better the conductivity, but the increase in conductivity after hot pressing for more than 30 minutes is not significant, so the hot pressing time Should be controlled within 30 minutes.
步驟106是清洗，是將具有導電薄膜的基材片36先置於去離子水中潤洗5~30分鐘，並浸泡2小時換水，重複5次，再浸泡乙醇2小時，再於溫度60℃下抽真空，藉此可去除殘留在該導電薄膜中的界面活性劑，以免殘留雜質造成該導電薄膜的導電度降低。清洗完成並乾燥後，就能製得結合在該基材片36上的結合有金屬奈米粒子的奈米碳管複合物導電薄膜成品。Step 106 is cleaning. The substrate sheet 36 having a conductive film 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 a temperature of 60 ° C. A vacuum is applied, whereby the surfactant remaining in the conductive film can be removed to prevent the residual impurities from causing a decrease in the conductivity of the conductive film. After the cleaning is completed and dried, the finished carbon nanotube composite conductive film bonded to the metal nanoparticle is bonded to the substrate sheet 36.
值得一提的是，在步驟102除了只使用步驟101所製備的奈米碳管複合物配合溶劑調配為該奈米碳管複合物溶液外，也可以將預定比例的未結合金屬奈米粒子的純奈米碳管與結合有金屬奈米粒子的奈米碳管複合物一起混合加入該溶劑中調配成奈米碳管複合物溶液，及在步驟103中，該等霧化顆粒同時挾帶有該等奈米碳管複合物及該等純奈米碳管。藉此，以具有最佳負載效率的奈米碳管複合物與純奈米碳管相混合，仍可達到預期的導電效果，且能減少導電薄膜中金屬奈米粒子的使用量以降低成本。當二奈米碳管交疊時，只要單邊的奈米碳管具有金屬奈米粒子就能達到連接二奈米碳管的管壁而達到作為導電通道的效果，因此，混合奈米碳管複合物與純奈米碳管仍能達到預定的導電性。It is worth mentioning that, in step 102, in addition to using only the carbon nanotube composite prepared in step 101 to prepare a solution of the carbon nanotube complex with a solvent, a predetermined ratio of unbound metal nanoparticles may also be used. The pure carbon nanotubes are mixed with the carbon nanotube composite combined with the metal nanoparticles to be added into the solvent to prepare a nanocarbon tube composite solution, and in step 103, the atomized particles are simultaneously carried The carbon nanotube composites and the pure carbon nanotubes. Thereby, the carbon nanotube composite with the best load efficiency is mixed with the pure carbon nanotube to achieve the desired electrical conductivity, and the amount of metal nanoparticles used in the conductive film can be reduced to reduce the cost. When the two carbon nanotubes overlap, as long as the single-sided carbon nanotubes have the metal nanoparticles, the wall connecting the two carbon nanotubes can be achieved to achieve the effect as a conductive passage. Therefore, the carbon nanotubes are mixed. The composite and the pure carbon nanotubes still achieve a predetermined conductivity.
<具體例一-製備結合有鉑奈米粒子之奈米碳管複合物><Specific Example 1 - Preparation of Nano Carbon Tube Composites Bonded with Platinum Nanoparticles>
將150.2mg已純化與熱處理的奈米碳管在氮氣環境下利用超音波作用使其分散於100ml無水乙二醇溶液中，並將已充分溶解於100ml無水乙二醇中的K2 PtCl4 (79.9mg，無結晶水)，利用雙頭針在氮氣環境下將其轉移置入含奈米碳管之無水乙二醇分散液中，充分攪拌均勻後，以每分鐘上升2℃緩緩升溫至160℃，並恆溫2小時後結束反應。趁熱過濾收集所形成的奈米碳管複合物，並使用無水乙醇沖洗數次後，在80℃真空乾燥12小時，就能得到負載20wt%鉑奈米粒子的奈米碳管複合物A。另外，以前述同樣方法，但將K2 PtCl4 的量改為212.8mg則能得到負載40wt%鉑奈米粒子的奈米碳管複合物B。其中，上述的雙頭針的功能在於可以將兩個氮氣環境下溶液系統有效地由一邊轉移至另一邊，並且不接觸外界空氣，例如，抽血用的針頭，因其針頭一邊連接血管，一邊連接血袋，就是一種雙頭針。150.2 mg of purified and heat-treated carbon nanotubes were ultrasonically dispersed in 100 ml of anhydrous ethylene glycol solution under nitrogen atmosphere, and K 2 PtCl 4 (which was sufficiently dissolved in 100 ml of anhydrous ethylene glycol) 79.9mg, no crystal water), transferred to a non-aqueous ethylene glycol dispersion containing carbon nanotubes under a nitrogen atmosphere by a double-ended needle, and after fully stirring, the temperature is gradually raised by 2 ° C per minute. The reaction was terminated at 160 ° C and at a constant temperature of 2 hours. The formed carbon nanotube composite was collected by hot filtration and washed with absolute ethanol for several times, and then vacuum dried at 80 ° C for 12 hours to obtain a carbon nanotube composite A loaded with 20 wt% of platinum nanoparticles. Further, in the same manner as described above, the amount of K 2 PtCl 4 was changed to 212.8 mg to obtain a carbon nanotube composite B loaded with 40 wt% of platinum nanoparticles. Wherein, the function of the above-mentioned double-ended needle is that the solution system in two nitrogen atmospheres can be effectively transferred from one side to the other side, and does not contact the outside air, for example, a needle for blood drawing, because the needle is connected to the blood vessel side, Connecting the blood bag is a double-ended needle.
如圖3與圖4所示，分別為在穿透式電子顯微鏡(transmission electron microscope，簡稱為TEM)下所觀察到的負載20wt%鉑奈米粒子的奈米碳管複合物A，及負載40wt%鉑奈米粒子的奈米碳管複合物B的形貌，為有效表現鉑奈米粒子在奈米碳管管壁的附著性，奈米碳管複合物A、B皆分別以槽式超音波作用15分鐘後，再取澄清樣品進行TEM觀察的結果，顯示經超音波作用後，鉑奈米粒子仍然穩定地附著於奈米碳管上。此外，如圖5所示，為奈米碳管複合物A先以超音波分散，並經超音波霧化成霧化顆粒後沉積於TEM樣品載台的鍍碳銅網上，再以TEM觀察的結果，顯示鉑奈米粒子經過超音波震盪分散與霧化處理後，仍能結合於奈米碳管上，顯示其與奈米碳管管壁間具有極優異的附著力，據此可以說明本發明製法所形成的結合有金屬奈米粒子之奈米碳管複合物，能夠承受製成薄膜過程中所施加的超音波分散與霧化等處理程序，進而能順利地被製成該奈米碳管複合物導電薄膜產品。As shown in FIG. 3 and FIG. 4, respectively, a carbon nanotube composite A loaded with 20 wt% of platinum nanoparticles observed under a transmission electron microscope (TEM), and a load of 40 wt. The morphology of the carbon nanotube composite B of the % platinum nanoparticle is effective for the adhesion of the platinum nanoparticle to the wall of the carbon nanotube tube, and the carbon nanotube composites A and B are respectively grooved. After 15 minutes of sonication, the clarified sample was taken for TEM observation, and it was shown that the platinum nanoparticles remained attached to the carbon nanotubes stably after the ultrasonic action. In addition, as shown in FIG. 5, the carbon nanotube composite A is first dispersed by ultrasonic waves, and is atomized by ultrasonic waves into atomized particles and deposited on the carbon-coated copper mesh of the TEM sample stage, and then observed by TEM. As a result, it was revealed that the platinum nanoparticles were able to be bonded to the carbon nanotubes after being subjected to ultrasonic vibration dispersion and atomization treatment, and showed excellent adhesion to the carbon nanotube wall. The carbon nanotube composite combined with the metal nanoparticle formed by the invention method can withstand the processing procedures of ultrasonic dispersion and atomization applied during the film formation, and can be smoothly formed into the nano carbon. Tube composite conductive film products.
<具體例二-製備結合有鉑與銀奈米粒子之奈米碳管複合物><Specific Example 2 - Preparation of a carbon nanotube composite in which platinum and silver nanoparticles are combined>
將150.1mg已純化與熱處理之奈米碳管在氮氣環境下利用超音波作用使其分散於100ml無水乙二醇溶液中，並將已充分溶解於100ml無水乙二醇中的K2 PtCl4 (7.2mg，無結晶水)，利用雙頭針在氮氣環境下將其轉移置入含奈米碳管之無水乙二醇分散液中，充分攪拌均勻後，以每分鐘上子2℃緩緩升溫至160℃，並恆溫2小時。接著將該溶液冷卻到室溫後，再於氮氣環境下將已充分溶解AgNO3 (54.1mg)的無水乙二醇溶液加入，充分攪拌後，以每分鐘上升2℃緩慢升溫至160℃，並恆溫2小時後結束反應。趁熱過濾收集所形成的奈米碳管複合物，並使用無水乙醇沖洗數次後，在80℃真空乾燥12小時，就能得到負載20wt%鉑/銀奈米粒子的奈米碳管複合物C，其中，鉑與銀的重量比為1：10。150.1 mg of purified and heat-treated carbon nanotubes were ultrasonically dispersed in 100 ml of anhydrous ethylene glycol solution under nitrogen atmosphere, and K 2 PtCl 4 (which was sufficiently dissolved in 100 ml of anhydrous ethylene glycol) 7.2mg, no crystal water), use a double-headed needle to transfer it into the anhydrous ethylene glycol dispersion containing carbon nanotubes under nitrogen atmosphere, stir well, and then slowly heat up at 2 °C per minute. To 160 ° C, and constant temperature for 2 hours. After the solution was cooled to room temperature, an anhydrous glycol solution in which AgNO 3 (54.1 mg) was sufficiently dissolved was added under a nitrogen atmosphere, and after sufficiently stirring, the temperature was slowly raised to 160 ° C by 2 ° C per minute. The reaction was terminated after 2 hours of constant temperature. The formed carbon nanotube composite was collected by hot filtration and washed with absolute ethanol for several times, and then vacuum dried at 80 ° C for 12 hours to obtain a carbon nanotube composite loaded with 20 wt% of platinum/silver nanoparticles. C, wherein the weight ratio of platinum to silver is 1:10.
如圖6所示，為在穿透式電子顯微鏡(TEM)下所觀察到的負載20wt%鉑/銀奈米粒子的奈米碳管複合物C的形貌，由圖中可明顯觀察出奈米碳管的管壁上附著密集的金屬奈米粒子，顯示使用二種不同的金屬奈米粒子仍能達到附著於奈米碳管的管壁上的效果。As shown in Fig. 6, the morphology of the carbon nanotube composite C loaded with 20 wt% of platinum/silver nanoparticle observed under a transmission electron microscope (TEM) can be clearly observed from the figure. The dense metal nanoparticles attached to the tube wall of the carbon nanotube show that the effect of adhering to the wall of the carbon nanotube can still be achieved by using two different metal nanoparticles.
此外，當以能量分散光譜儀(energy dispersive spectrometer，簡稱為EDS)對奈米碳管複合物C進行量測，結果顯示其鉑與銀的重量比為8.85：91.15，與原始添加量的1：10極為接近，顯示以前述的二階段還原合成可以精確地控制金屬複合比例。In addition, when the carbon nanotube composite C was measured by an energy dispersive spectrometer (EDS), the weight ratio of platinum to silver was 8.85:91.15, and the original addition amount was 1:10. Very close, showing that the metal complex ratio can be precisely controlled by the two-stage reduction synthesis described above.
分別對奈米碳管複合物A、B、C、純化的奈米碳管(Pure CNT)及原始未純化奈米碳管(Raw CNT)進行熱重量分析，其中，是以10℃/min的升溫速率，在空氣條件下升溫至900℃，其結果如圖7所示，奈米碳管複合物A、B的殘餘量分別為21.9%與42.2%，其最後殘餘的金屬比例與原始所用金屬化合物在該奈米碳管複合物所佔的比例相比極為接近，顯示鉑奈米粒子與奈米碳管管壁間有極佳的作用力故能獲得高負載比率，所測得的殘餘量超過原來添加的鉑離子重量比例20wt%與40wt%應為部分殘餘的石墨與鉑金屬結合，難以在900℃空氣環境下氧化揮發所致。另外，以二階段還原所製得的結合有鉑與銀奈米粒子的奈米碳管複合物C則可能由於初始還原濃度過低，導致最後殘餘金屬比例略低於其原來所添加的金屬比例，但其殘餘金屬比例仍相當接近原始所用金屬化合物在該奈米碳管複合物所佔的比例，顯示以二階段還原製得的結合有鉑與銀奈米粒子的奈米碳管複合物C也能獲得高金屬奈米粒子負載比率。Thermogravimetric analysis of carbon nanotube composites A, B, C, purified carbon nanotubes (Pure CNT) and raw unpurified carbon nanotubes (Raw CNT), respectively, at 10 ° C / min The heating rate was raised to 900 ° C under air conditions. The results are shown in Fig. 7. The residual amounts of the carbon nanotube composites A and B were 21.9% and 42.2%, respectively, and the final residual metal ratio and the original metal used. The proportion of the compound in the carbon nanotube composite is very close, showing that the platinum nanoparticle and the carbon nanotube wall have excellent interaction, so that a high load ratio can be obtained, and the measured residual amount More than 20% by weight and 40% by weight of the originally added platinum ion should be partially residual graphite combined with platinum metal, which is difficult to oxidize and volatilize in an air environment of 900 ° C. In addition, the carbon nanotube complex C combined with platinum and silver nanoparticles prepared by two-stage reduction may have a lower initial residual concentration, resulting in a ratio of the final residual metal slightly lower than the proportion of the originally added metal. However, the residual metal ratio is still quite close to the proportion of the original metal compound in the carbon nanotube composite, showing the carbon nanotube complex C combined with platinum and silver nanoparticles prepared by two-stage reduction. High metal nanoparticle loading ratios can also be obtained.
<具體例三-金屬奈米粒子附著率測試><Specific Example 3 - Metal Nanoparticle Adhesion Test>
以<具體例一> 的方法分別製備負載10wt%、20wt%、40wt%鉑奈米粒子的奈米碳管複合物，及以<具體例二> 的方法分別就鉑與銀的重量比為1：5、1：10及1：20三種情況，各製備負載10wt%、20wt%、40wt%鉑/銀奈米粒子的奈米碳管複合物，將前述奈米碳管複合物分別以高溫爐750℃灰化並量測殘餘的金屬重量(相當於附著於奈米碳管上的金屬奈米粒子總重)，並將該重量除以起始所添加的金屬鹽化合物中的金屬離子重量，其結果為金屬奈米粒子的總附著率，並將實驗結果整理如下表1。The carbon nanotube composites loaded with 10 wt%, 20 wt%, and 40 wt% of platinum nanoparticles were separately prepared by the method of <Specific Example 1> , and the weight ratio of platinum to silver was 1 by the method of <Specific Example 2> . : 5, 1:10 and 1:20, each preparation of carbon nanotube composites loaded with 10wt%, 20wt%, 40wt% platinum/silver nanoparticles, the above-mentioned carbon nanotube composites respectively in a high temperature furnace Ashing at 750 ° C and measuring the weight of the residual metal (corresponding to the total weight of the metal nanoparticles attached to the carbon nanotubes), and dividing the weight by the weight of the metal ions in the initially added metal salt compound, The result was the total adhesion rate of the metal nanoparticles, and the experimental results were summarized in Table 1 below.
根據表1的結果，在考量高附著率與原料成本(減少鉑的用量)的情形下，顯示20wt%鉑/銀奈米粒子的奈米碳管複合物，當Pt：Ag=1：10時，可在相對較少的鉑用量下獲得最佳的金屬奈米粒子附著率。According to the results of Table 1, in the case of considering high adhesion rate and raw material cost (reducing the amount of platinum), a carbon nanotube composite showing 20 wt% of platinum/silver nanoparticle was observed, when Pt:Ag = 1:10. The best metal nanoparticle adhesion rate can be obtained with a relatively small amount of platinum.
<具體例四-製備結合有金屬奈米粒子之奈米碳管複合物<Specific Example 4 - Preparation of Nano Carbon Tube Composites Bonded with Metal Nanoparticles 導電薄膜並進行耐曲撓性測試>Conductive film and test for flexural resistance >
(1)分別製備如下四種樣品：樣品I：純化的奈米碳管、樣品II：以<具體例一> 所示的方式製備20wt%金奈米粒子的奈米碳管複合物(其中金屬鹽化合物為HAuCl4 ，用量為65.2mg)、樣品III：20wt%鉑/銀奈米粒子的奈米碳管複合物(Pt：Ag=1：10)，及樣品IV：由20wt%鉑/銀奈米粒子的奈米碳管複合物III(Pt：Ag=1：10)與不含金屬奈米粒子的純奈米碳管以1：1的比例混合所得到的奈米碳管混合物(相當於10wt%鉑/銀奈米粒子的奈米碳管複合物)。(1) The following four samples were prepared separately: Sample I: purified carbon nanotubes, sample II: carbon nanotube composites prepared with 20 wt% of gold nanoparticles in the manner shown in <Specific Example 1 (where metal The salt compound is HAuCl 4 in an amount of 65.2 mg), the sample III: 20 wt% platinum/silver nanoparticle nanotube complex (Pt: Ag = 1:10), and the sample IV: from 20 wt% platinum/silver The carbon nanotube mixture obtained by mixing the carbon nanotube composite III (Pt: Ag = 1:10) of the nanoparticle with the pure carbon nanotube containing no metal nanoparticle in a ratio of 1:1 (equivalent a carbon nanotube composite of 10 wt% platinum/silver nanoparticle).
(2)分別將前述四種樣品I~IV配置成10mg/L的奈米碳管複合物溶液：分別於1L的去離子水中投入10mg的樣品I~IV及10mg的SDS，可先以功率750W的探頭式超音波震盪分散器(機型：Sonics ＆ Materials,Inc.「SONICSVCX750」)對該奈米碳管複合物溶液以20%功率作用5分鐘，及30%功率作用5分鐘，以防止該等奈米碳管複合物聚集並呈均勻分散的狀態。(2) The above four samples I~IV were respectively arranged into a 10 mg/L carbon nanotube complex solution: 10 mg of sample I~IV and 10 mg of SDS were respectively added to 1 L of deionized water, and the power was first 750 W. Probe-type ultrasonic oscillator diffuser (model: Sonics & Materials, Inc. "SONICS The VCX 750") was applied to the carbon nanotube composite solution at 20% power for 5 minutes and at 30% power for 5 minutes to prevent the carbon nanotube composites from aggregating and uniformly dispersed.
(3)霧化：將超音波霧化器置於液面下3.0cm的深度處，並使溶液的溫度維持在30℃，提供1.65MHz的超音波霧化頻率作用於該奈米碳管複合物溶液，則可達到25~30ml/hr的霧化率，且霧化顆粒的粒徑約為3μm，利用一與盛裝樣品I~IV溶液的容器相連通的輸氣管送入攜帶氣體，該攜帶氣體的流速為22L/min。(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 provided to act on the carbon nanotube composite. The solution solution can reach an atomization rate of 25 to 30 ml/hr, and the atomized particles have a particle diameter of about 3 μm, and the carrier gas is fed into the gas pipe connected to the container containing the sample I~IV solution, and the carrier is carried. The gas flow rate was 22 L/min.
(4)旋轉塗佈：該攜帶氣體將該等霧化顆粒引導到一旋轉塗佈機的基座上，於該基座上放置的基材片是與該基座同步旋轉，進行旋轉塗佈前，該基材片是先於500r.p.m.的轉速下以去離子水清洗40秒，再於800r.p.m.的轉速下以酒精清洗60秒，再進行該等超音波霧化顆粒的旋轉塗佈。(4) spin coating: the carrier gas guides the atomized particles onto a susceptor of a spin coater, and the substrate sheet placed on the susceptor is rotated synchronously with the susceptor for spin coating Before, the substrate sheet was washed with deionized water for 40 seconds at a speed of 500 rpm, and then washed with alcohol at a speed of 800 rpm for 60 seconds, and then spin coating of the ultrasonic atomized particles. .
進行超音波霧化顆粒的旋轉塗佈時，是先經一次濕潤旋轉塗佈與一次初步成膜旋轉塗佈的預處理，再重複進行多次周期性的再成膜旋轉塗佈。其中，進行濕潤旋轉塗佈的轉速為300r.p.m與450r.p.m.相交替數次，進行初步成膜旋轉塗佈的轉速則為自450r.p.m.依階梯式上升到6000r.p.m.後，再進入周期性的再成膜旋轉塗佈。塗佈進行的過程中，該基座是以如圖9所示的階段式周期進行連續旋轉，且區間(I)表示濕潤旋轉塗佈的轉速變化，區間(II)表示初步成膜旋轉塗佈的階梯式轉速變化，區間(III)、(IV)、(V)皆為再成膜旋轉塗佈的階梯式轉速變化，藉此，使該等霧化顆粒能較均勻地塗佈至該基材片表面，且能透過旋轉塗佈的時間長短控制該奈米碳管複合物導電薄膜的成膜厚度。在圖9中，不同階段別分別以不同字母表示，並將其所代表的轉速與時間整理如下表2，表2中各階段的時間不應受限，可再依實際需求進行調整。When the spin coating of the ultrasonic atomized particles is performed, the pretreatment is performed by one wet spin coating and one preliminary film spin coating, and the periodic recoating spin coating is repeated a plurality of times. Among them, the rotational speed of the wet spin coating is 300r.pm and 450r.pm alternately, and the rotational speed of the preliminary film spin coating is from 450r.pm to 6000r.pm, and then enters the cycle. Sex 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 forming spin coating. The stepwise speed change, the sections (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 the spin coating. In Figure 9, the different stages are represented by different letters, and the speed and time represented by them are organized as shown in Table 2 below. The time of each stage in Table 2 should not be limited, and can be adjusted according to actual needs.
旋轉塗佈的時間是控制在10分鐘~60分鐘，以藉由控制旋轉塗佈的時間讓所形成的多層壁奈米碳管導電薄膜能達到設計的規格，其中，主要是藉由調整c~f的時間來調整該奈米碳管複合物導電薄膜的厚度。The spin coating time is controlled from 10 minutes to 60 minutes to control the spin coating time to achieve the design specifications of the multilayered nano-carbon nanotube conductive film, which is mainly by adjusting c~ The time of f is used to adjust the thickness of the conductive film of the carbon nanotube composite.
(5)熱壓：將一熱壓機的上下壓模的溫度升溫至70℃，並維持恆溫1小時，並將溫度的上下變動控制在±0.25℃以下，裁剪四片5cm×5cm的PET薄片，並分別以去離子水、乙醇、去離子水、丙酮、去離子水的清洗順序潤洗該等PET薄片，再以上下各二片的方式夾住已設置有該導電薄膜(分別由樣品I~IV所製成)的基材片，再取10cm×10cm的不銹鋼夾具上下疊合於PET薄片外，並將組合完成的基材片、PET薄片與不銹鋼夾具一起置於該熱壓機的上下壓模之間，並施加100kg/cm2 的壓力熱壓30分鐘。(5) Hot pressing: the temperature of the upper and lower stampers of a hot press is raised to 70 ° C, and the temperature is maintained for 1 hour, and the temperature fluctuation is controlled below ± 0.25 ° C, and four pieces of 5 cm × 5 cm PET sheets are cut. And rinsing the PET sheets in a cleaning sequence of deionized water, ethanol, deionized water, acetone, deionized water, respectively, and sandwiching the two conductive sheets to form the conductive film (sample I, respectively) a substrate sheet made of ~IV, and then a 10 cm×10 cm stainless steel jig is superposed on the PET sheet, and the combined substrate sheet, PET sheet and stainless steel jig are placed on top of the hot press. Between the stampers, a pressure of 100 kg/cm 2 was applied and hot pressed for 30 minutes.
(6)清洗：以前述步驟106所述的方式清洗熱壓完成的導電薄膜基材片，就能分別製得奈米碳管導電薄膜I(由樣品I所製成)，及結合有金屬奈米粒子的奈米碳管複合物導電薄膜II~IV(分別由樣品II~IV所製成)。(6) Cleaning: The hot-pressed conductive film substrate sheet is cleaned in the manner described in the foregoing step 106, and the carbon nanotube conductive film I (made of the sample I) can be separately obtained, and the metal naphthalene is combined. The carbon nanotube composite conductive film II~IV of rice particles (made of samples II~IV, respectively).
<耐曲撓性測試><Flexibility test>
參閱圖8，將所製得的附有導電薄膜I~IV的基材片裁成1cm×2cm的試片51，並量測該試片51未受彎折前的導電度。接著，將該試片51較長邊的二相反側分別固定至一固定夾座52，及一與該固定夾座51相間隔的活動夾座53之間，再使該活動夾座53靠向該固定夾座51位移至該試片51長邊的二相反側的間距為1cm，再進一步位移到該試片51長邊的二相反側的間距為0.5cm為止，該試片51會隨著該活動夾座53的活動而曲撓彎折，接著，再使該活動夾座53遠離該固定夾座52位移，並使該試片51回復為平直狀態，量測該試片51受彎折後的片電阻，重複前述使該試片51曲撓彎折的動作，且該試片51每次回復到平直狀態後都再測一次片電阻，藉由片電阻的變化可相應地反應出導電度的變化，片電阻值越穩定顯示導電度也較穩定。Referring to Fig. 8, the obtained substrate sheet with conductive films I to IV was cut into a test piece 51 of 1 cm × 2 cm, and the conductivity of the test piece 51 before being bent was measured. Then, the opposite sides of the longer side of the test piece 51 are respectively fixed to a fixed clip 52, and a movable clip 53 spaced apart from the fixed clip 51, and the movable clip 53 is biased toward the opposite side. The fixing clip 51 is displaced to the opposite side of the long side of the test piece 51 by a distance of 1 cm, and further displaced to a distance of 0.5 cm on the opposite side of the long side of the test piece 51, the test piece 51 will follow The movement of the movable clamp 53 is bent and bent, and then the movable clamp 53 is displaced away from the fixed clamp 52, and the test piece 51 is returned to a flat state, and the test piece 51 is measured to be bent. The folded sheet resistance repeats the above-described operation of flexing and bending the test piece 51, and the test piece 51 is again measured once after returning to the flat state, and the sheet resistance can be correspondingly reacted by the change of the sheet resistance. The change in conductivity, the more stable the sheet resistance value, the more stable the conductivity.
由於前面幾次的曲撓，會使導電薄膜的片電阻皆呈不穩定的變化，無法作明確的比較，因此，先分別將導電薄膜I~IV的試片各折彎50次使其片電阻(導電度)穩定後，再正式進入耐曲撓性測試。其中，折彎50次後穩定的片電阻值分別為導電薄膜I(CNT/PET)≒3KΩ/□，導電薄膜II(20%Au-CNT/PET)≒157Ω/□，導電薄膜III(20%Ag/Pt-CNT/PET)≒175Ω/□，及導電薄膜IV(10% Ag/Pt-CNT/PET)≒229Ω/□，並將折彎100次、250次及500次所測得的片電阻分別與折彎50次的片電阻比較，結果如下表3所示：Due to the previous several flexings, the sheet resistance of the conductive film is unstable, and it is impossible to make a clear comparison. Therefore, the test pieces of the conductive films I~IV are respectively bent 50 times to make the sheet resistance. After the (conductivity) is stabilized, it is officially entered into the flexural resistance test. Among them, the sheet resistance values after stabilization for 50 times are conductive film I (CNT/PET) ≒ 3K Ω / □, conductive film II (20% Au-CNT / PET) ≒ 157 Ω / □, conductive film III (20%) Ag/Pt-CNT/PET) ≒175Ω/□, and conductive film IV (10% Ag/Pt-CNT/PET) ≒229Ω/□, and the film measured by bending 100 times, 250 times and 500 times The resistance is compared with the sheet resistance of bending 50 times, and the results are shown in Table 3 below:
測試結果顯示CNT/PET試片曲撓100次後的片電阻上升10%，曲撓250次後的片電阻上升20%，曲撓500次後的片電阻上升20%，而結合有金屬奈米粒子的奈米碳管複合物所製成的導電薄膜II~IV的試片，不但其折彎50次穩定後的片電阻值比CNT/PET試片低，且其經由100次、250次、500次折彎後片電阻的變化率也降低至3%以下，甚至幾乎沒有變化，顯示於奈米碳管摻雜高導電性的金屬奈米粒子並製成導電薄膜後，具有更佳的耐曲撓性，據此可說明結合有金屬奈米粒子之奈米碳管複合物導電薄膜除了可藉由該等金屬奈米粒子降低奈米碳管間的接觸電阻而提高導電效能外，也有助於提升導電薄膜結構的穩定性。The test results show that the sheet resistance of the CNT/PET test piece is increased by 10% after 100 times of bending, the sheet resistance of the sheet after the bending of 250 times is increased by 20%, and the sheet resistance after the bending of 500 times is increased by 20%, and the metal nanometer is combined. The test piece of the conductive film II~IV made of the carbon nanotube composite of the particle not only has a sheet resistance lower than that of the CNT/PET test piece after being bent 50 times, and it passes 100 times, 250 times, After 500 bends, the rate of change of sheet resistance is also reduced to 3% or less, or even almost no change. It is shown that the carbon nanotubes are doped with highly conductive metal nanoparticles and made into a conductive film, which has better resistance to bending. Flexibility, according to this, it can be explained that the conductive film of the carbon nanotube composite combined with the metal nanoparticle can also improve the electrical conductivity by reducing the contact resistance between the carbon nanotubes by the metal nanoparticles, and also contributes to Improve the stability of the conductive film structure.
一般可供應用的導電薄膜的片電阻值規格範圍是在10~800Ω/cm2 ，一般觸控式面板所用導電薄膜的片電阻規格則在200~800Ω/cm2 ，由以上的結果說明本發明所製出的導電薄膜的片電阻值已符合應用規格，而具有實際應用的價值。The sheet resistance value of the conductive film generally applicable is in the range of 10 to 800 Ω/cm 2 , and the sheet resistance of the conductive film used in the general touch panel is 200 to 800 Ω/cm 2 , and the present invention is explained by the above results. The sheet resistance of the produced conductive film has met the application specifications and has practical application value.
歸納上述，本發明結合有金屬奈米粒子之奈米碳管複合物導電薄膜的製法，可獲致下述的功效及優點，故能達到本發明的目的：In summary, the present invention combines the production method of a carbon nanotube composite conductive film of metal nanoparticles to obtain the following effects and advantages, thereby achieving the object of the present invention:
一、由於奈米碳管與奈米碳管間僅有極少的接觸面積，使碳管間的接觸電阻遠高於奈米碳管薄膜其他可能的電阻而成為主要電阻來源，藉由使預定量的金屬奈米粒子附著結合至奈米碳管上，可於管壁形成接觸點形成有效的高導電通道，且表面粗糙並附著金屬奈米粒子的奈米碳管複合物所形成的導電薄膜，其接觸電阻易因外力變化而大幅降低，使本發明製法所製得的奈米碳管複合物導電薄膜能有效提升其導電效能，而具有商業化應用的價值。1. Since there is only a small contact area between the carbon nanotubes and the carbon nanotubes, the contact resistance between the carbon tubes is much higher than other possible resistances of the carbon nanotube film and becomes the main source of resistance by making a predetermined amount. The metal nanoparticle adheres to the carbon nanotube, and forms a conductive film formed by forming a contact point on the tube wall to form an effective high-conductivity channel and having a rough surface and adhering the carbon nanotube composite of the metal nanoparticle. The contact resistance is easily reduced by the change of external force, so that the carbon nanotube composite conductive film prepared by the method of the invention can effectively improve the electrical conductivity and has the value of commercial application.
二、藉由配製結合有金屬奈米粒子的奈米碳管複合物溶液，再提供特定的超音波頻率使奈米碳管複合物溶液形成霧化顆粒，並透過攜帶氣體使其塗佈於一旋轉的基材片上，就能製得厚度均勻的導電薄膜，顯示本發明能以容易取得的設備及較簡便的製程製出低電阻且具有更佳導電性能的奈米碳管複合物導電薄膜，而具有製程較簡化能符合實用與經濟效益的優點。2. By preparing a carbon nanotube composite solution combined with metal nanoparticles, and providing a specific ultrasonic frequency, the nanocarbon tube composite solution is formed into atomized particles, and coated by a carrier gas. On the rotating substrate sheet, a conductive film having a uniform thickness can be obtained, which shows that the present invention can produce a low-resistance and better conductive carbon nanotube composite conductive film in a readily available device and a relatively simple process. The simplified process can meet the advantages of practical and economic benefits.
三、由耐曲撓性測試的結果說明以本發明製造方法所製得的導電薄膜經多次曲撓後，其導電度仍然符合所要求的應用規格，使本發明製造方法能夠製得具有較佳耐曲撓性且結構更穩定的導電薄膜。3. The results of the flexural resistance test show that the conductive film prepared by the manufacturing method of the present invention has a plurality of flexural properties, and the electrical conductivity thereof still meets the required application specifications, so that the manufacturing method of the present invention can be produced. A conductive film that is flexible and structurally more stable.
四、可利用旋轉塗佈的時間長短控制最終所製得的導電薄膜的厚度，以對應製造出不同穿透率與不同電阻規格的導電薄膜，使本發明製造方法能以較簡單的控制方式調整製品的品質，以搭配不同等級的應用產品使用。4. The thickness of the finally obtained conductive film can be controlled by the length of the spin coating to correspondingly produce conductive films with 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.
惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍，即大凡依本發明申請專利範圍及發明說明內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。The above is only the preferred embodiment of the present invention, and the scope of the 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 remain within the scope of the invention patent.
30．．．奈米碳管複合物溶液30. . . Nano carbon tube composite solution
31．．．霧化顆粒31. . . Atomized particle
32．．．攜帶氣體32. . . Carrying gas
33．．．霧化容器33. . . Atomizing container
34．．．虹吸管34. . . siphon
35．．．超音波元件35. . . Ultrasonic component
36．．．基材片36. . . Substrate sheet
37．．．基座37. . . Pedestal
38．．．貯液容器38. . . Liquid container
39．．．升降座39. . . Lifting seat
51．．．導電薄膜試片51. . . Conductive film test piece
52．．．固定夾座52. . . Fixed clamp
53．．．活動夾座53. . . Activity holder
圖1是一說明本發明結合有金屬奈米粒子之奈米碳管複合物導電薄膜的製法一較佳實施例的流程圖；1 is a flow chart showing a preferred embodiment of a method for producing a conductive film of a carbon nanotube composite incorporating a metal nanoparticle according to the present invention;
圖2是一示意圖，說明在該較佳實施例中所使用的裝置的組合情形；Figure 2 is a schematic view showing the combination of the devices used in the preferred embodiment;
圖3是一穿透式電子顯微鏡照像圖，說明多數個金屬(鉑)奈米粒子結合於奈米碳管上的情形；Figure 3 is a transmission electron microscope photograph showing the case where a plurality of metal (platinum) nanoparticles are bonded to a carbon nanotube;
圖4是一穿透式電子顯微鏡照像圖，說明多數個金屬(鉑)奈米粒子結合於奈米碳管上的情形；Figure 4 is a transmission electron microscope photograph showing the case where a plurality of metal (platinum) nanoparticles are bonded to a carbon nanotube;
圖5是一穿透式電子顯微鏡照像圖，說明多數個金屬(鉑)奈米粒子結合於奈米碳管上的情形；Figure 5 is a transmission electron microscope photograph showing the case where a plurality of metal (platinum) nanoparticles are bonded to a carbon nanotube;
圖6是一穿透式電子顯微鏡照像圖，說明多數個金屬(鉑/銀)奈米粒子結合於奈米碳管上的情形；Figure 6 is a photomicrograph of a transmission electron microscope illustrating the case where a plurality of metal (platinum/silver) nanoparticles are bonded to a carbon nanotube;
圖7是一曲線圖，說明奈米碳管複合物樣品A、B、C經熱重量分析的結果；Figure 7 is a graph showing the results of thermogravimetric analysis of carbon nanotube composite samples A, B, and C;
圖8是一示意圖，說明以本發明製法所製出的導電薄膜試片進行曲撓性測試的過程；及Figure 8 is a schematic view showing the process of conducting a flexural test on a conductive film test piece produced by the method of the present invention; and
圖9是一曲線示意圖，說明該較佳實施例進行旋轉塗佈時，不同時間所設定轉速的變化情形。Fig. 9 is a schematic view showing the change of the rotational speed set at different times when the preferred embodiment performs spin coating.
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| Hao Tong, Hu-Lin Li, Xiao-Gang Zhang (2007)"Ultrasonic synthesis of highly dispersed Pt nanoparticles supported on MWCNTs and their electrocatalytic activity towards methanol oxidation" Carbon 45 pp. 2424–2432 * |
| Zhijuan Wang, Qixian Zhang, Dan Kuehner, Xiaoyu Xu, Ari Ivaska, Li Niu (2008/7) "The synthesis of ionic-liquid-functionalized multiwalled carbon nanotubes decorated with highly dispersed Au nanoparticles and their use in oxygen reduction by electrocatalysis" CARBON 46 pp. 1687–1692 * |
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| TWI649444B (en) * | 2016-07-11 | 2019-02-01 | 東芝三菱電機產業系統股份有限公司 | Droplet coating film forming device and droplet coating film forming method |
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