TWI409828B - 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 not sufficiently soft and has relatively poor durability and relatively low reliability in use.
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，特別是透光與導電性能是目前研究的二大重點，藉此能再進一步提升產品使用性能，並更精進製程技術而能有效降低生產成本。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 factor. Therefore, there is still a need to continuously develop different types of material technologies and improve the performance of existing materials, especially light transmission and Conductivity is the second major focus of the current research, which can further improve the product performance, and more precise nin-cycle technology can effectively reduce production costs.
因此，本發明的目的，是在提供一種製程較簡化且能再進一步提升透光與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。Accordingly, an object of the present invention is to provide a method for producing a carbon nanotube composite conductive film incorporating metal nanoparticles in which the process is simplified and the light transmission and electrical conductivity are 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；(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 to transport the atomized particles along a predetermined path, wherein the atomized particles have a particle size 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；及(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; and
(v)將該奈米碳管複合物導電薄膜放置在一腔室中進行微波後處理，以提升其透光率與導電性能。(v) placing the carbon nanotube composite conductive film in a chamber for microwave post-treatment to enhance its light transmittance and electrical conductivity.
本發明的有益效果在於：以奈米碳管配合金屬鹽化合物能製備出結合有金屬奈米粒子且具有較佳導電性能的奈米碳管複合物薄膜，再配合能快速升溫且能迅速移除熱源的微波後處理，使該等金屬奈米粒子能再融合進而能有效黏著與固定於奈米碳管管壁交疊處，使本發明不但能利用超音波霧化與旋轉塗佈的方式，以較簡便的設備與製程技術製出具較佳導電性能的導電薄膜，還能透過微波後處理再進一步提升該導電薄膜的透光率並降低其電阻。The invention has the beneficial effects that the carbon nanotube composite film combined with the metal nano particles and having better conductivity can be prepared by using the carbon nanotube compound with the metal salt compound, and the mixture can rapidly heat up and can be quickly removed. The microwave post-treatment of the heat source enables the metal nanoparticles to re-melt and effectively adhere and fix at the intersection of the carbon nanotube wall, so that the invention can not only utilize ultrasonic atomization and spin coating. The conductive film with better conductivity can be produced by simple equipment and process technology, and the light transmittance of the conductive film can be further improved and the electric resistance can be reduced by microwave post-treatment.
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、圖2與圖3，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, FIG. 2 and FIG. 3, a preferred embodiment of the method for preparing a carbon nanotube composite conductive film incorporating metal nanoparticle particles according to the present invention comprises the following steps: Step 101 is to respectively apply a predetermined amount of a metal salt compound. Dissolved in a dry ethylene glycol to prepare a first solution, and a predetermined amount of carbon nanotubes dissolved in an anhydrous ethylene glycol to prepare a dispersion, and then mixed and stirred for each minute. Increasing the temperature rise rate of 2 ° C ~ 5 ° C to 100 ° C ~ 160 ° C and maintaining a constant temperature for 1-3 hours, so that the metal ions in the metal salt compound are reduced to metal nanoparticles and attached to the carbon nanotubes, After forming a plurality of carbon nanotube composites combined with metal nanoparticles, the mixture is directly filtered hot, washed with absolute ethanol for several times, and vacuum dried at a temperature of 80 ° C to obtain the nanometers. Carbon tube composite. 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100。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. On the surface, a conductive film 100 is uniformly formed.
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100的基材片36施加預定壓力，用以使該導電薄膜100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100的表面電阻，使該導電薄膜100能表現更佳的導電度。Step 105 is hot pressing, applying a predetermined pressure to the substrate sheet 36 provided with the conductive film 100 at a predetermined temperature, so that the conductive film 100 is compacted and formed into a denser and stable structure, and The formation of a tighter bond between the carbon nanotube composites helps to reduce the surface resistance of the conductive film 100, so that the conductive film 100 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100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100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100成品。Step 106 is cleaning. The substrate sheet 36 having the conductive film 100 is firstly rinsed in deionized water for 5 to 30 minutes, and immersed for 2 hours for water exchange, repeated 5 times, and then immersed 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 100 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 100 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100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 having the best load efficiency is mixed with the pure carbon nanotube to achieve the desired electrical conductivity, and the amount of the metal nanoparticle in the conductive film 100 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.
步驟107是將數片具有導電薄膜100的基材片36放置在一微波裝置4的一腔室410中進行微波後處理，以提升其透光率與導電性能。由於金屬材料的融點往往遠高於高分子軟性基板(例如，PET基板)所能承受的極限溫度，因此，所採用的後處理方法必須在高分子軟性基板可承受的製程條件下進行，藉此，較佳是採用能快速升溫並能迅速移除熱源的方法進行後處理，一方面，能藉由加熱奈米碳管及附著其上的金屬奈米粒子達到促進其金屬奈米粒子彼此相融合及提升金屬-奈米碳管管壁交界面的附著性目的，另一方面，又能透過迅速降溫而減少餘熱對高分子基板的熱破壞。其中，以微波方式進行後處理具有能改善光電效能與不需昂貴的設備成本的實用價值與經濟效益。在本實施例中，是在壓力大於等於250torr的環境下進行微波加熱(microwave heating)處理。微波加熱的處理方法，具有能快速升溫與迅速移除熱源的特性，除了能達到加熱熔融金屬奈米粒子的目的外，還可藉由迅速降溫減少餘熱以避免對高分子材質的基材片36造成熱破壞。由於微波為高能量加熱源，因此微波後處理的處理時間較佳是限制在3分鐘以內。以下就微波熱處理方法做進一步說明：微波加熱：將具有導電薄膜100的基材片36置於該微波裝置4的一反應腔體41的腔室410中，並以一抽氣單元42對該腔室410抽真空，再透過一供氣單元43提供一選自下列群組中的氣體5至該腔室410：氮氣、氬氣、氦氣、氧氣、氫氣以及空氣，藉此使該腔室410維持預定壓力。在本實施例中，較佳是在壓力大於等於250torr的惰性氣體環境下進行微波加熱，但是，也可以不進行抽真空再供氣的過程，而直接在一般室內常壓下進行微波加熱處理，同樣能改善該導電薄膜100的透光率與導電性能。其中，是藉由一發射微波單元44在一段預定的時間長度內，持續對該腔室410提供一微波能量，並透過該氣體5作用至該導電薄膜100。本實施例中所用的發射微波單元44的功率為750W，且使用時實質上是將其頻率設定為2.45GHz，所用的發射源則是磁控管。In step 107, a plurality of substrate sheets 36 having a conductive film 100 are placed in a chamber 410 of the microwave device 4 for microwave post-treatment to enhance 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 preferred to carry out post-treatment by a method capable of rapidly increasing the temperature and rapidly removing the heat source. On the one hand, the metal nanoparticles can be promoted by heating the carbon nanotubes and the metal nanoparticles attached thereto. It combines and enhances the adhesion of the metal-nano carbon tube wall interface. On the other hand, it can reduce the thermal damage of the polymer substrate to the polymer substrate by rapidly cooling. 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, microwave heating treatment is performed in an environment having a pressure of 250 torr or more. The microwave heating treatment method has the characteristics of rapid temperature rise and rapid removal of the heat source. In addition to the purpose of heating the molten metal nanoparticles, the residual heat can be reduced by rapid cooling to avoid the substrate sheet of the polymer material. Causes thermal damage. Since the microwave is a high-energy heating source, the processing time of the microwave post-treatment is preferably limited to within 3 minutes. The microwave heat treatment method is further described below: microwave heating: a substrate sheet 36 having a conductive film 100 is placed in a chamber 410 of a reaction chamber 41 of the microwave device 4, and the chamber is evacuated by a pumping unit 42. The chamber 410 is evacuated, and a gas 5 selected from the following group is supplied to the chamber 410 through a gas supply unit 43: nitrogen, argon, helium, oxygen, hydrogen, and air, thereby causing the chamber 410. Maintain the predetermined pressure. In the present embodiment, it is preferred to perform microwave heating in an inert gas atmosphere having a pressure of 250 torr or more, but it is also possible to perform microwave heating treatment directly under normal indoor atmospheric pressure without performing a process of vacuuming and supplying air. The light transmittance and electrical conductivity of the conductive film 100 can also be improved. Wherein, a microwave energy is continuously supplied to the chamber 410 by a transmitting microwave unit 44 for a predetermined period of time, and the conductive film 100 is applied through the gas 5. The power of the transmitting microwave unit 44 used in this embodiment is 750 W, and the frequency is substantially set to 2.45 GHz when used, and the source used is a magnetron.
值得說明的是，經微波加熱處理而製得較佳透光率與導電性能的導電薄膜100後，還能配合一形成有一預定鏤空圖紋或電路圖案的遮蔽件(圖未示)遮蓋該導電薄膜100的部分區域，再對該導電薄膜100進行微波電漿加熱處理，則該奈米碳管複合物導電薄膜100未被該遮蔽件遮住的區域中，未受金屬奈米子吸附或包覆的奈米碳管部分受微波電漿作用而汽化揮發，在該導電薄膜100上形成選擇性蝕刻的結果，並使該區域形成無法傳導電流的區域，而被遮蔽的區域則形成能用以傳導電流的電路線路圖，利用此種方式可在該導電薄膜100上產生預定的電路圖案，具有可供實際製程應用的價值。其中，微波電漿加熱除了壓力條件外，其他條件與前述的微波加熱處理類似，故不再贅述。進行微波電漿加熱時，是先對該腔室410抽真空，再提供氣體使該腔室的壓力維持在0.1torr~2.0torr。It should be noted that after the conductive film 100 having better light transmittance and conductivity is obtained by microwave heat treatment, a shielding member (not shown) formed with a predetermined hollow pattern or circuit pattern can cover the conductive portion. A portion of the film 100 is subjected to microwave plasma heat treatment of the conductive film 100, and the carbon nanotube composite conductive film 100 is not adsorbed or coated by the metal nano-particles in a region not covered by the shielding member. The carbon nanotube portion is vaporized and volatilized by the action of microwave plasma, and a selective etching result is formed on the conductive film 100, and the region is formed into a region where the current cannot be conducted, and the shielded region is formed to be conductive. A circuit diagram of the current in which a predetermined circuit pattern can be produced on the conductive film 100 has a value for practical process applications. Among them, the microwave plasma heating is similar to the microwave heating treatment described above except for the pressure conditions, and therefore will not be described again. When microwave plasma heating is performed, the chamber 410 is first evacuated, and gas is supplied to maintain the pressure of the chamber at 0.1 torr to 2.0 torr.
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HAuCl4 (65.2mg)，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A，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%金奈米粒子的奈米碳管複合物。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 HAuCl 4 (65.2 mg) which was sufficiently dissolved in 100 ml of anhydrous ethylene glycol. The double-headed needle is transferred into a non-aqueous ethylene glycol dispersion containing a carbon nanotube under a nitrogen atmosphere, and after being sufficiently stirred, the temperature is gradually raised to 160 ° C by 2 ° C per minute, and the temperature is constant 2 The reaction was terminated after an hour. The formed carbon nanotube composite A 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 gold 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5所示，為前述奈米碳管複合物A進一步製成導電薄膜後，量測其微波加熱處理前、後的可見光光譜穿透率，顯示微波加熱處理前的導電薄膜在波長575nm處具有代表金屬奈米粒子特徵的表面電漿共振吸收峰，即該表面電漿共振吸收峰的出現說明在該導電薄膜中確實存在有金奈米粒子，據此可合理推測金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，因此，在以該奈米碳管複合物A所製得的導電薄膜上仍可觀察到表面電漿共振吸收峰。據此也可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. 5, after the carbon nanotube composite A is further formed into a conductive film, the visible light spectral 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. The surface plasma resonance absorption peak representing the characteristics of the metal nanoparticle, that is, the appearance of the surface plasma resonance absorption peak indicates that gold nanoparticles are indeed present in the conductive film, and accordingly, the gold nanoparticle can be reasonably estimated to be super After the sound wave is dispersed and atomized, it can still be bonded to the carbon nanotubes, which shows excellent adhesion to the carbon nanotube wall. Therefore, it is made of the carbon nanotube composite A. The surface plasma resonance absorption peak was still observed on the obtained conductive film. According to this, the carbon nanotube composite combined with the metal nanoparticle formed by the method of the present invention can be subjected to the processing procedures of ultrasonic dispersion and atomization applied during the film formation, and can be smoothly processed. The carbon nanotube composite conductive film product is produced.
(1)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A(其中金屬鹽化合物為HAuCl4 ，用量為65.2mg)為樣品I。(1) A carbon nanotube composite A (in which a metal salt compound was HAuCl 4 in an amount of 65.2 mg) of 20 wt% of gold nanoparticles was prepared as Sample I in the manner shown in <Specific Example 1> .
(2)將該樣品I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、II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 sample I was configured as a 10 mg/L carbon nanotube complex solution: 10 mg of sample I, II, and 10 mg of SDS were separately charged in 1 L of deionized water, and the probe type ultrasonic wave of 750 W was first used. Shock 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、II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 and II 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-1，表-1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-1 below. The time of each stage in Table-1 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，就能製得結合有金奈米粒子的奈米碳管複合物導電薄膜I(由樣品I所製成)。(6) Cleaning: The hot-pressed conductive film substrate sheet is cleaned in the manner described in the foregoing step 106, and a carbon nanotube composite conductive film I (made of sample I) combined with the gold nanoparticle particles can be obtained. to make).
<微波加熱處理前後的變化情形><Changes before and after microwave heating treatment>
(1)微波熱處理前：將<具體例二-製備結合有金奈米粒子之奈米碳管複合物導電薄膜>所製得的結合有金奈米粒子的奈米碳管複合物導電薄膜I裁成數片1cm×2cm的試片，並先量測其未受微波熱處理前的可見光譜透光率、在波長550nm時的透光率及片電阻。(1) Before the microwave heat treatment: the carbon nanotube composite conductive film I bonded with the gold nanoparticle prepared by <Specific Example 2 - Preparation of the carbon nanotube composite conductive film bonded with the gold nanoparticle> A plurality of test pieces of 1 cm × 2 cm were cut, and the visible light transmittance before the microwave heat treatment, the light transmittance at a wavelength of 550 nm, and the sheet resistance were measured first.
(2)將該導電薄膜I的試片置入如圖3所示微波裝置4中進行微波加熱處理，處理條件為壓力250torr，微波作用時間90秒，經微波加熱後，再量測導電薄膜I的試片的可見光譜透光率、在波長550nm時的透光率及片電阻。(2) The test piece of the conductive film I is placed in the microwave device 4 as shown in FIG. 3 for microwave heating treatment under the conditions of a pressure of 250 torr, a microwave action time of 90 seconds, and after microwave heating, the conductive film I is measured. The visible light transmittance of the test piece, the light transmittance at a wavelength of 550 nm, and the sheet resistance.
需要補充說明的是，由於經微波熱處理後該導電薄膜I的試片中的金奈米粒子的粒徑仍小於10nm，所以無法藉由掃描式電子顯微鏡(簡稱為SEM)觀察奈米碳管管壁表面的金奈米粒子的實際形貌變化，而穿透式電子顯微鏡(簡稱為TEM)樣品載台(鍍碳銅網)在微波環境下，會發生嚴重的電弧放電(arc discharge)的破壞現象，因此也無法以TEM觀察。僅能透過X-光粉末繞射光譜(X-ray powder diffraction spectrum，簡稱為XRD)中的峰值位置(角度)、半高峰寬度值與謝樂方程式(Scherrer equation)來計算奈米粒子粒徑大小(B. D. Cullity,S. R. Stock,Elements of X-ray Diffraction .,4th,Chapter 5,Prentice-Hall(2001)、C. Gervais,M. E. Smith,A. Pottier,J. P. Jolivet,F. Babonneau.‘Solid-State 47,49Ti NMR Determination of the phase Distribution of Titania Nanoparticles’.Chem. Mater .,13 ,462(2001)、C. Aletru,G. N. 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 Scattering’.J. Phys. Chem. B .,103 ,4147(1999))或由表面電漿共振效應來推測微波加熱處理前、後的細部形貌變化。It should be noted that since the particle size of the gold nanoparticles in the test piece of the conductive film I after the microwave heat treatment is still less than 10 nm, the carbon nanotube tube cannot be observed by a scanning electron microscope (SEM). The actual morphology of the gold nanoparticles on the wall surface changes, and the transmission electron microscope (referred to as TEM) sample carrier (carbon coated copper mesh) in the microwave environment, severe arc discharge damage Phenomenon, therefore, can not be observed by TEM. The particle size of the nanoparticles can be calculated only by the peak position (angle), the half-peak width value and the Scherrer equation in the X-ray powder diffraction spectrum (XRD). (BD Cullity, SR Stock, Elements of X-ray Diffraction ., 4th, Chapter 5, Prentice-Hall (2001), C. Gervais, ME Smith, A. Pottier, JP Jolivet, F. Babonneau. 'Solid-State 47 , 49Ti NMR Determination of the phase Distribution of Titania Nanoparticles'. 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 Scattering'. J. Phys. Chem. B. , 103 , 4147 (1999)) or by surface plasma resonance effect It is estimated that the topography changes before and after microwave heating treatment.
參閱圖5，為前述導電薄膜I的試片在微波加熱處理前後所分別量測到的可見光光譜透光率變化曲線，由圖5可看出經微波加熱後，該導電薄膜I的試片的透光率顯著改善，此外，還可觀察到未經微波加熱前，該導電薄膜I的試片中的金奈米粒子的表面電漿共振吸收峰相較於傳統溶液相金奈米粒子520nm的表面電漿共振吸收峰(H. S. Zhou,I. Honma,H. Komiyama,‘Controlled synthesis and quantum-size effect in gold-coated nanoparticles’,Phys. Rev. B ,50 ,12052(1994)、Marie-Christine Daniel,Didier Astruc,‘Gold 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 Spectroscopy’,J. Phys. Chem. C ,113 ,4277(2009))，對該導電薄膜試片I進行可見光光譜穿透率量測所得的表面電漿吸收峰，其波峰已紅移至575nm，應為金奈米粒子吸附在奈米碳管管壁表面所致。經微波加熱處理後，其波峰則明顯藍移且訊號比迅速降低，此變化結果顯示附著在奈米碳管管壁的金奈米粒子在經過微波加熱處理後，可能因融熔而呈現攤平狀態並包覆於奈米碳管的管壁上，因而難以維持完整的奈米顆粒形貌，亦導致以SEM顯微鏡檢測時，難以明顯觀察出金奈米粒子的形貌，進而造成所量測到的光譜呈現表面電漿共振吸收峰訊號快速減弱的現象。再參閱圖6與圖7，分別為經微波熱處理前、後結合有金奈米粒子之奈米碳管複合物導電薄膜的局部放大的SEM圖，其中較光亮的部分為吸附在奈米碳管的金奈米粒子，雖然無法很明顯地觀察奈米碳管管壁表面的金奈米粒子的實際形貌變化，但藉由比較圖6與圖7中光亮部分的分布情形，仍可看出經微波加熱後，金奈米粒子自呈顆粒狀的附著狀態轉變成攤平包覆在奈米碳管管壁上的現象，且有部分光亮部分似有融入奈米碳管管壁的情形，說明可能有部分熔融的金奈米粒子滲入奈米碳管管壁，藉此，可再提升奈米碳管的導電性，也有助改善由該奈米碳管複合物所製成的導電薄膜的導電性能。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 nanoparticles in the test piece of the conductive film I before the microwave heating is 520 nm compared with the conventional solution phase gold nanoparticles. Surface plasmon resonance absorption peaks (HS Zhou, I. Honma, H. Komiyama, 'Controlled synthesis and quantum-size effect in gold-coated nanoparticles', Phys. Rev. B , 50 , 12052 (1994), Marie-Christine Daniel , Didier Astruc, 'Gold 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, 'Siz e Evaluation of Gold Nanoparticles by UV-vis Spectroscopy', 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 Its peak has been red-shifted to 575nm, which should be caused by the adsorption of gold nanoparticles 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 difficult to observe the morphology of the gold nanoparticles when the SEM microscope is used, thereby causing the measurement. The resulting spectrum shows a phenomenon in which the surface plasma 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 nanoparticles, although it is not possible to observe the actual shape change of the gold nanoparticles on the surface of the carbon nanotube wall, by comparing the distribution of the bright parts in Fig. 6 and Fig. 7, it can be seen After microwave heating, the gold nanoparticles are transformed into a granular coating on the wall of the carbon nanotube tube, and some bright parts appear to be integrated into the wall of the carbon nanotube tube. It is indicated that some molten gold nanoparticles may penetrate into the wall of the carbon nanotube tube, thereby further improving the conductivity of the carbon nanotube, and also helping to improve the conductive film made of the carbon nanotube composite. Conductive properties.
另外，該導電薄膜I在微波加熱處理前後的片電阻與550nm透光率的結果如下：In addition, the sheet resistance of the conductive film I before and after the microwave heat treatment and the light transmittance at 550 nm are as follows:
由此結果顯示經微波熱處理可同步降低試片的片電阻至未處理前的38%，550nm透光率則可提升17%，據此結果可明確證實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，還能藉由微波加熱處理，再進一步提升該導電薄膜的透光率與導電性能。The results show that the microwave heat treatment can simultaneously 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 the results, the carbon nanotubes combined with the metal nanoparticles can be clearly confirmed. In addition to improving the electrical conductivity by reducing the contact resistance between the carbon nanotubes by the metal nanoparticles, the composite conductive film can further improve the light transmittance and conductivity of the conductive film by microwave heat treatment. .
<微波電漿加熱的影響><Impact of Microwave Plasma Heating>
將<具體例二-製備結合有金奈米粒子之奈米碳管複合物導電薄膜>所製得的結合有金奈米粒子的奈米碳管複合物導電薄膜I裁成數片1cm×2cm的試片，並分別以(i)0.7torr的空氣電漿作用30秒，(ii)以0.7torr的空氣電漿作用60秒。接著，再以SEM顯微鏡觀察經前述條件處理後導電薄膜試片的形貌變化。The specific carbon nanotube composite conductive film I prepared by the specific example 2 - preparing the carbon nanotube composite conductive film bonded with the gold nanoparticle is cut into several pieces of 1 cm × 2 cm The test piece was treated with (i) 0.7 torr air plasma for 30 seconds, and (ii) with 0.7 torr air plasma for 60 seconds. Next, the morphology change of the conductive film test piece after the above conditions were observed by an SEM microscope.
如圖8、圖9所示，分別經條件(i)、(ii)處理後所獲得的SEM圖，由圖8可看出以0.7torr的空氣電漿作用30秒處理後，該導電薄膜試片中未完整包覆金奈米粒子的奈米碳管在高能量電漿環境下被蝕刻而汽化揮發，最後使得薄膜表面形成不連續的線狀結構。如圖9所示，顯示再延長電漿作用時間為60秒，且同樣以0.7torr的空氣電漿作用後，該導電薄膜試片中的奈米碳管幾乎被蝕刻殆盡，最後剩下密集排列的金奈米粒子。As shown in Fig. 8 and Fig. 9, the SEM images obtained after the conditions (i) and (ii), respectively, can be seen from Fig. 8 after the air plasma treatment of 0.7 torr for 30 seconds, the conductive film test The carbon nanotubes in the sheet which are not completely coated with the gold nanoparticles are etched in a high-energy plasma environment to vaporize and volatilize, and finally a discontinuous linear structure is formed on the surface of the film. As shown in Fig. 9, after the re-extension plasma action time is 60 seconds, and the same is applied to the air plasma of 0.7 torr, the carbon nanotubes in the conductive film test piece are almost etched, and finally the dense Arranged gold nanoparticles.
經由前述試驗結果顯示，奈米碳管複合物導電薄膜，得以在微波電漿作用的環境下，輕易地達到選擇性蝕刻的結果。因此，奈米碳管複合物導電薄膜在後續應用上，得以配合電漿乾式光阻蝕製程，取代ITO透光導電薄膜濕式蝕刻製程(wet etching process)，所能獲得的透光導電薄膜相關應用電子元件，而極具發展潛力。此外，由圖9可觀察到結合在奈米奈米碳管上的金奈米粒子經微波電漿蝕刻作用後，其金奈米粒子形貌近似球形，且仍可穩約觀察到金奈米粒子有沿著奈米碳管分布網絡呈現線形排列的傾向，此現象如配合直立式奈米碳管的奈米圖案(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. Phys. Chem. C ,111 ,17879(2007))或直線形奈米碳管的自組裝排列(Jun Matsui,Kohei Yamamoto,Nobuhiro Inokuma,Hironori Orikasa,Takashi Kyotania,Tokuji Miyashita,‘Fabrication of densely packed multi-walled carbon nanotube ultrathin films using a liquid-liquid interface’,J. Mater. Chem .,17 ,3806(2007))，將有機會組裝高密度且具方向性排列的金奈米粒子陣列，而有可應用在光學感測器與電化學感測器上的發展潛力。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, in the subsequent application, the carbon nanotube composite conductive film can be combined with the plasma dry photo-etching process to replace the ITO transparent conductive film wet etching process, which can be obtained by the transparent conductive film. The application of electronic components 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. Phys. Chem. C , 111 , 17879 (2007)) or self-assembled arrangement of linear carbon nanotubes (Jun Matsui) , Kohei Yamamoto, Nobuhiro Inokuma, Hironori Orikasa, Takashi Kyotania, Tokuji Miyashita, 'Fabrication of densely packed multi-walled carbon nanotube ultrathin films using a liquid-liquid interface', J. Mater. Chem ., 17 , 3806 (2007) It will have the opportunity to assemble high-density and directional arrays of gold nanoparticle arrays with potential for application in optical sensors and electrochemical sensors.
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，再配合微波後處理，能夠利用微波能快速升溫與迅速移除熱源的特性，在避免高分子材質的基材片36不受熱破壞的先決條件下，促進相鄰近的金屬奈米粒子彼此相融合，並有效提升金屬奈米粒子與奈米碳管管壁交界面的附著性，藉以再進一步提升該導電薄膜的透光率與降低其電阻，使本發明製法能藉由結合金屬奈米粒子與微波後處理的方式，達到大幅提升導電薄膜透光率與導電效能的結果，而具有能進一步改善產品性能的實用價值。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 nanoparticles are attached to the carbon nanotubes to form an effective high-conductivity channel at the contact points of the tube wall, and then combined with microwave post-treatment, which can utilize the rapid heating of the microwave energy and the rapid removal of the heat source, thereby avoiding Under the precondition that the polymer substrate sheet 36 is not damaged by heat, the adjacent metal nanoparticles are promoted to fuse with each other, and the adhesion between the metal nanoparticles and the carbon nanotube wall is effectively enhanced, thereby re Further improving the light transmittance of the conductive film and reducing the electrical resistance thereof, so that the method of the present invention can achieve the result of greatly improving the light transmittance and the conductive performance of the conductive film by combining the metal nanoparticles and the microwave post-treatment. Further improve the practical value of product performance.
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，再配合容易取得的微波設備就能顯著改善該導電薄膜的性能，顯示本發明能以容易取得的設備及較簡便的製程製出具有更佳透光率與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, and the performance of the conductive film can be significantly improved by the easy-to-obtain microwave device, which shows that the present invention can be produced with easy-to-obtain equipment and a relatively simple process. Better conductivity and conductivity of the carbon nanotube composite conductive film, and the process is simplified to meet the practical and economic benefits.
三、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。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.
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 Complex Solution
31‧‧‧霧化顆粒31‧‧‧Atomized particles
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 components
36‧‧‧基材片36‧‧‧Substrate film
37‧‧‧基座37‧‧‧Base
38‧‧‧貯液容器38‧‧‧Liquid container
39‧‧‧升降座39‧‧‧ Lifting seat
100‧‧‧導電薄膜100‧‧‧Electrical film
4‧‧‧微波裝置4‧‧‧Microwave device
41‧‧‧反應腔體41‧‧‧Reaction chamber
410‧‧‧腔室410‧‧‧ chamber
42‧‧‧抽氣單元42‧‧‧Pumping unit
43‧‧‧供氣單元43‧‧‧ gas supply unit
44‧‧‧發射微波單元44‧‧‧Transmission microwave unit
5‧‧‧氣體5‧‧‧ gas
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進行霧化與旋轉塗佈所使用的一裝置的組合情形；Figure 2 is a schematic view showing the combination of a device used for atomization and spin coating in the preferred embodiment;
圖3是一是一示意圖，說明在該較佳實施例進行微波後處理所使用的一微波裝置的情形；Figure 3 is a schematic view showing the state of a microwave device used for microwave post-processing in the preferred embodiment;
圖4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；Figure 4 is a schematic view showing the change of the set rotational speed at different times when the preferred embodiment performs spin coating;
圖5是一曲線圖，說明本發明製法所製出的導電薄膜試片於微波加熱處理前後的可見光光譜透光率變化情形；Figure 5 is a graph showing the change of visible light transmittance of the conductive film test piece prepared by the method of the present invention before and after microwave heating treatment;
圖6是一掃描式電子顯微鏡照像圖，說明本發明製法所製出的導電薄膜試片於微波加熱處理前的情形；6 is a scanning electron microscope photograph showing the state of the conductive film test piece prepared by the method of the present invention before microwave heating treatment;
圖7是一掃描式電子顯微鏡照像圖，說明本發明製法所製出的導電薄膜試片於微波加熱處理後的變化情形；7 is a scanning electron microscope photograph showing the change of the conductive film test piece produced by the method of the present invention after microwave heating treatment;
圖8是是一掃描式電子顯微鏡照像圖，說明以0.7torr的微波電漿作用30秒後，該導電薄膜試片上之奈米碳管與金奈米粒子的形貌變化情形；及Figure 8 is a scanning electron microscope photograph showing the morphology change of the carbon nanotubes and the gold nanoparticles on the conductive thin film test piece after being subjected to microwave plasma treatment of 0.7 torr for 30 seconds;
圖9是一掃描式電子顯微鏡照像圖，說明以0.7torr的微波電漿作用60秒後，該導電薄膜試片之奈米碳管與金奈米粒子的形貌變化情形。Fig. 9 is a scanning electron microscope photograph showing the morphology change of the carbon nanotubes and the gold nanoparticles of the conductive film test piece after 60 seconds of microwave plasma treatment of 0.7 torr.
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